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Title:
SUPRAMOLECULAR COMPOUNDS AND THEIR USE AS ANTITUMOUR AND ANTIVIRAL AGENTS
Document Type and Number:
WIPO Patent Application WO/2005/033119
Kind Code:
A1
Abstract:
The application discloses the use of supramolecular compounds as antitumour, antimicrobial (such as antibacterial and antiprotozoal) and antiviral agents. Such compounds comprise ligands as defined in the application coordinated to at least two metal ions. Pharmaceutical formulations and detergent formulations are also disclosed.

Inventors:
Hannon, Michael (Department of Chemistry, University of Warwick Gibbet Hill Road, Coventry CV4 7AL, GB)
Rodger, Alison (Department of Chemistry, University of Warwick Gibbet Hill Road, Coventry CV4 7AL, GB)
Mann, Nicholas Harold (20 Waller Street, Leamington Spa, Warwickshire CV32 5UP, GB)
Application Number:
PCT/GB2004/004227
Publication Date:
April 14, 2005
Filing Date:
October 04, 2004
Export Citation:
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Assignee:
UNIVERSITY OF WARWICK (Gibbet Hill Road, Coventry CV4 7AL, GB)
Hannon, Michael (Department of Chemistry, University of Warwick Gibbet Hill Road, Coventry CV4 7AL, GB)
Rodger, Alison (Department of Chemistry, University of Warwick Gibbet Hill Road, Coventry CV4 7AL, GB)
Mann, Nicholas Harold (20 Waller Street, Leamington Spa, Warwickshire CV32 5UP, GB)
International Classes:
C07D213/53; C07D213/77; C07D215/12; C07D233/54; C07D241/12; C07F1/00; C07F13/00; C07F15/02; C07F15/04; C07F15/06; (IPC1-7): C07F17/02; C07D213/53; C07D213/77; C07D215/12; C07D233/54; C07D241/12; C07F19/00
Other References:
FLORIANA TUNA ET AL.: "The effect of phenyl substituents on supramolecular assemblies containing directly linked bis-pyridylimine ligands: synthesis and structural characterisation of mononuclear nickel(II) and dinuclear silver(I) and cobalt (III) complexes of (2-pyridyl)phenylketazine" DALTON TRANSACTIONS., no. 11, 28 May 2003 (2003-05-28), pages 2149-2155, XP002314446 GBROYAL SOCIETY OF CHEMISTRY, CAMBRIDGE.
FLORIANA TUNA ET AL.: "Metalo-supramolecular libraries:triangles, polymers and double-helicates assembled by copper(I)coordination to directly linked bis-pyridinylimine ligands" DALTON TRANSACTIONS., no. 11, 28 May 2003 (2003-05-28), pages 2141-2148, XP002314447 GBROYAL SOCIETY OF CHEMISTRY, CAMBRIDGE.
JACQUELINE HAMBLIN ET AL.: "Triple helictes and planar dimers arising from silver(I)coordination to directly linked bis-pyridylimine ligands" DALTON TRANSACTIONS., no. 8, 11 April 2002 (2002-04-11), pages 1635-1641, XP002314448 GBROYAL SOCIETY OF CHEMISTRY, CAMBRIDGE. cited in the application
ARNAUD LAVALETTE ET AL.: "Interfacing supramolecular and macromolecular chemistry: metallo-supramolecular triple-helicates incorporated into polymer networks" CHEMICAL COMMUNICATIONS, no. 24, 29 November 2002 (2002-11-29), pages 3040-3041, XP002314449 SEINSTITUTE OF INORGANIC AND PHYSICAL CHEMISTRY, STOCKHOLM,
LAURA J. CHILDS ET AL.: "Assembly of Nano-Scale Circular Supramolecular Arrays through pi-pi Aggregation of Arc-Shaped Helicate units" ANGEWANDTE CHEMIE. INTERNATIONAL EDITION., vol. 40, no. 6, 16 March 2001 (2001-03-16), pages 1079-1081, XP002314450 DEVCH VERLAG, WEINHEIM. cited in the application
LAURA J. CHILDS ET AL.: "Assembly of a Nanoscale Chiral Ball through Supramolecular Aggregation of Bowl-Shaped Triangular Helicates" ANGEWANDTE CHEMIE. INTERNATIONAL EDITION., vol. 41, no. 22, 15 November 2002 (2002-11-15), pages 4244-4247, XP002314451 DEVCH VERLAG, WEINHEIM. cited in the application
MICHAEL. J. HANNON ET AL.: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION., vol. 40, no. 5, 2 March 2001 (2001-03-02), pages 879-884, XP002314452 DEVCH VERLAG, WEINHEIM. cited in the application
MICHAEL J. HANNON ET AL.: "Spacer control of Directionality in Supramolecular Helicates Using an Inexpensive Approach" ANGEWANDTE CHEMIE. INTERNATIONAL EDITION., vol. 38, no. 9, 1999, pages 1277-1278, XP002314453 DEVCH VERLAG, WEINHEIM. cited in the application
MICHAEL J. HANNON ET AL.: "A metallo-supramolecular double-helix containing a major and a minor groove" CHEMICAL COMMUNICATIONS, no. 20, 1999, pages 2023-2024, XP002314454 SEINSTITUTE OF INORGANIC AND PHYSICAL CHEMISTRY, STOCKHOLM, cited in the application
ISABELLE MEISTERMANN ET AL.: "Intramolecular DNA coiling mediated by metallosupramolecular cylinders: Differential binding of P and M helical enantiomers" PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES, vol. 99, no. 8, 16 April 2002 (2002-04-16), pages 5069-5074, XP002314455 USNATIONAL ACADEMY OF SCIENCE, WASHINGTON, DC cited in the application
JACQUELINE HAMBLIN ET AL.: "Directed one-pot syntheses of enantiopure dinuclear silver(i) and copper(i) metallo-supramolecular double helicates" DALTON TRANSACTIONS., no. 2, 10 January 2002 (2002-01-10), pages 164-169, XP002314456 GBROYAL SOCIETY OF CHEMISTRY, CAMBRIDGE. cited in the application
Attorney, Agent or Firm:
Elsy, David (Withers & Rogers LLP, Goldings House 2 Hays Lane, London SE1 2HW, GB)
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Claims:
Claims
1. 1 A method of inhibiting tumour, microbial or viral growth comprising contacting a tumour, microbe or virus with an effective amount of a supramolecular compound, or a pharmaceutically acceptable salt, derived from a ligand (L) of formula I or a ligand of formula II,: Formula I Wherein: Each X for formula I may the same or different and may be C or N, wherein when X=N, there is no R group attached to X; or Formula II : indicates a 5 membered heterocycle such as imidazole, pyrazole, thiazole, oxazole wherein X in formula II may be the same or different and may be C or N, or X can be NH, S, O, in which case the R group is absent; and wherein RI to R8 may be independently selected from H, OAlkyl, OAryl, CH20Alkyl, CH20Aryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, COzH, CO2Alkyl, CO2Aryl, O, CH2O, CO2, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2Alkyl, OSO2Aryl, O2Aryl, SO2Me, N (Alkyl)2 and Alkyne ; Z = CH, CAlkyl, CAryl, or CNHz and may be the same or different Y may be present or not present and may be selected from: R may be selected from H, OAlkyl, OAryl, CH20AIkyl, CH20Aryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CHZOH, C02H C02AIkyls COzAt 0, CH20, CO2, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2Alkyl, OSO2Aryl, SO2Me, N (Alkyl) 2 and Alkyne; A = NH, S, SO2, O, (CH2)n, CHR, CR2, or NR and R is as defined above n = an integer 1,2, 3,4, 5,... 20 coordinated to at least 2 metal ions 2) A method of treating a tumour, a microbial infection or a viral infection comprising the step of administering a pharmaceutically effective amount of a supramolecular compound, or a pharmaceutically acceptable salt, derived from a ligand (L) of formula I or a ligand of formula II,: Formula I Wherein : Each X for formula I may the same or different and may be C or N, wherein when X=N, there is no R group attached to X; or Formula II: indicates a 5 membered heterocycle such as imidazole, pyrazole, thiazole, oxazole wherein X in formula II may be the same or different and may be C or N, or X can be NH, S, O, in which case the R group is absent; and wherein RI to R8 may be independently selected from H, OAlkyl, OAryl, CH2OAlkyl, CH20Aryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, COZH, CO2Alkyl, COZAryI, O, CH20, C02, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2Alkyl, OSO2Aryl, O2Aryl, SO2Me, N (Alkyl) 2 and Alkyne ; Z = CH, CAlkyl, CAryl, or CNH2 and may be the same or different Y may be present or not present and may be selected from: Wherein: R may be selected from H, OAlkyl, OAryl, CH2OAlkyl, CH2OAryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, COzH, CO2Alkyl, CO2Aryl, O, CH20, CO2, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2Alkyl, OSO2Aryl, SO2Me, N (Alkyl) 2 and Alkyne; A = NH, S, SO2, O, (CH2) n, CHR, CR2, or NR and R is as defined above. n = an integer 1,2, 3,4, 5,... 20 coordinated to at least two metal ions 3) A supramolecular compound, or a pharmaceutically acceptable salt, derived from a ligand (L) of formula I or a ligand of formula II,: Formula I Wherein : Each X for formula I may the same or different and may be C or N, wherein when X=N, there is no R group attached to X; or Formula II: indicates a 5 membered heterocycle such as imidazole, pyrazole, thiazole, oxazole wherein X in formula II may be the same or different and may be C or N, or X can be NH, S, O, in which case the R group is absent; and wherein RI to R8 may be independently selected from H, OAlkyl, OAryl, CH2OAlkyl, CH2OAryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, COZH, CO2Alkyl, COiAryl, O, CH20, CO2, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2Alkyl, OSO2Aryl, O2Aryl, SO2Me, N (Alkyl) 2 and Alkyne ; Z = CH, CAlkyl, CAryl, or CNH2 and may be the same or different Y may be present or not present and may be selected from: R may be selected from H, OAlkyl, OAryl, CH20Alkyl, CH20Aryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, C02H, CO2Alkyl, CO2Aryl, O, CH2O, CO2, Alkyl, Aryl, BR, Cl, I, F, CN, N02, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OS02Alkyl, OSO2Aryl, SO2Me, N (Alkyl) 2 and Alkyne ; A = NH, S, SO2, Os (CH2) n, CHR, CR2, orNR and R is as defined above. n = an integer 1, 2,3, 4,5,... 20 coordinated to at least two metal ions for use as a therapeutic agent more preferably for use to treat a tumour, a microbial infection or a viral infection, 4) Method or compound according to any preceding claim, wherein the ligand of Formula I or Formula II is coordinated to a metal ions are selected from one or more of selected from Fez+, Fe3+, Nia+, Co2+, Co, Cu+, Cu2+, Ag+, Cd2+, Zn2+, Ru2+, Ru3+, Rh3+, Mn2+, Mn3+, Ir+, Ir2+, Ir3+, Os2+, Os3+, Pd2+, Pd3+, Pd4+, Pt2+, and Pt4+.
2. Method or compound according to any preceding claim, wherein the compound comprising the Ligand coordinated to the metal ions is defined by the general formula: Mn Lm where n and m are integers of 2 to 20, preferably 2,3, 4 or 5 and n and m may be the same or different.
3. Method or compound according to any preceding claim, wherein the compound is in combination with a pharmaceutically acceptable carrier, adjuvant or vehicle.
4. A supramolecular compound, or a pharmaceutically acceptable salt, derived from a ligand (L) of formula I or a ligand of formula II, : Formula I Wherein : Each X for formula I may the same or different and may be C or N, wherein when X=N, there is no R group attached to X; or Formula II: indicates a 5 membered heterocycle such as imidazole, pyrazole, thiazole, oxazole wherein X in formula II may be the same or different and may be C or N, or X can be NH, S, O, in which case the R group is absent; and wherein Rl to R8 may be independently selected from H, OAlkyl, OAryl, CH2OAlkyl, CH20Aryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, CO2H, CO2Alkyl, CO2Aryl, O, CH2O, CO2, Alkyl, Aryl, BR, Cl, I, F, CN, NOz, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2AIkyI, OSO2Aryl, OzAryl, SO2Me, N (Alkyl) 2 and Alkyne; Z = CH, CAlkyl, CAryl, or CNHz and may be the same or different Y may be present or not present and may be selected from: R may be selected from H, OAlkyl, OAryl, CH2OAIkyI, CH2OAryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, CO2H, CO2Alkyl, COzAryl, O, CH20, CO2, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2Alkyl, OSO2Aryl, SO2Me, N (Alkyl) 2 and Alkyne; A = NH, S, SO2, O, (CH2) n, CHR, CR2, or NR and R is as defined above. n = an integer 1,2, 3,4, 5,... 20 coordinated to at least two metal ions, in combination with a pharmaceutically acceptable carrier, adjuvant or vehicle 8) A disinfectant formulation comprising a supramolecular compound, or a pharmaceutically acceptable salt, derived from a ligand (L) of formula I or a ligand of formula II, coordinated to at least two metal ions : Formula I Wherein: Each X for formula I may the same or different and may be C or N, wherein when X=N, there is no R group attached to X ; or Formula II: indicates a 5 membered heterocycle such as imidazole, pyrazole, thiazole, oxazole wherein X in formula II may be the same or different and may be C or N, or X can be NH, S, O, in which case the R group is absent; and wherein Rl to R8 may be independently selected from H, OAlkyl, OAryl, CH2OAlkyl, CH2OAryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, CO2H, CO2Alkyl, CO2Aryl, O, CH20, CO2, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2Alkyl, OSO2Aryl, 02Aryl, SO2Me, N (Alkyl) 2 and Alkyne; Z = CH, CAlkyl, CAryl, or CNH2 and may be the same or different Y may be present or not present and may be selected from: R may be selected from H, OAlkyl, OAryl, CH20Alkyl, CH20Aryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, CO2H, COzAlkyl, CO2Aryl, O, CH20, CO2, Alkyl, Aryl, BR, Cl, I, F, CN, NOz, CF3, SAlkyl, SAryl, CH2SAlkyl, CHaSAryl, OSO2AIkyl, OSO2Aryl, SO2Me, N (Alkyl) 2 and Alkyne ; A = NH, S, SO2, O, (CH2) n, CHR, CR2, or NR and R is as defined above. n = an integer 1,2, 3,4, 5,... 20 coordinated to at least two metal ions 9) A combination or formulation according to claim 7 or claim 8, wherein the ligand of Formula I or Formula II is coordinated to a metal ions are selected from one or more of selected from Fe2+, Fe3+, Ni2+, Co2+, Co3+, Cu+, Cu2+, Ag+, Cd2+, Zn2+, Ru2+, Ru3+, Rh3+, Mn2+, Mn3+, Ir+, jr2+, Ir3+, Os2+, Os3+, Pd and Pd3+.
5. A combination or formulation according to claim 7 or claim 8,, wherein the compound comprising the Ligand coordinated to the metal ions is defined by the general formula: Mn Lm where n and m are integers of 2 to 20, preferably 2,3, 4 or 5 and n and m may be the same or different.
6. A method, compound or formulation according to any preceding claim, wherein the ligand is selected from a ligand shown in Figure 1 or Figure 2 12) A compound for use in the production of a supramolecular compound, selected from a compound shown in Figure 5 13) A supramolecular compound comprising a ligand selected from a compound shown in Figure 5 coordinated to at least two metal ions.
Description:
SUPRAMOLECULAR COMPOUNDS AND THEIR USE AS ANTITUMOUR AND ANTIVIRAL AGENTS The present invention relates to antitumour, antimicrobial (such as antibacterial and antiprotozoal) and antiviral agents, and more specifically to the use of supramolecular compounds as antitumour, antimicrobial (such as antibacterial and antiprotozoal) and antiviral agents.

Each year, cancer alone is responsible for nearly 500,000 deaths in the U. S. , making it the second leading cause of death in that country.

Traditional chemotherapeutic and radiotherapeutic agents target DNA but have low tumour to normal cell specificities. The former gives a number of disbenefits to the patient and the latter exposes the healthcare patient to a radiation dose. The drug usually also has a short shelf life once it has been formulated into a preparation.

The use of metal based drugs, such as transition metal (e. g. Fe, Pt) complexes (e. g.

Platinum (II) based cisplatin), are well known for use as therapeutic agents for cancer and viruses. The chemotherapeutic efficacy of cisplatin is derived from its ability to bind and crosslink DNA.

However, there is a need for new metallo-drugs with different modes of action because cis-platin has a limited spectrum of activity, toxic side effects and patients treated with the drug acquire resistance.

Supramolecular compounds are complex structures formed by the interaction of metal ions with ligands based on, for example bis (pyridylimine) and imidazolimines, as ligands, to form a system containing more than one metal ion and a number of ligands.

Such structures are often cylindrical helical, double helical or"triple helical"in shape.

See for example Hannon M. J. et al., 2001, Angew Chem Int Ed 40, pages 1079-1080, Hannon et al. 1999 Angew Chem Int Ed 38, pages 1277-1278, Supramolecular compounds are capable of binding to DNA. Hannon M and Rodger A. discuss DNA binding in Pharmaceutical Visions, 2002 (Autumn Edition), pages 14-16.

Nucleic acids, such as DNA, and indeed RNA, can form complex double, and indeed triple helical structures. Such structures often have a so-called major groove and minor groove running around the outside of the helix. The paper discusses sequence specific interactions of compounds such as proteins, and nucleic acids such as DNA oligonucleotides, synthetic molecules such as intercalators and molecules as targeting the major groove of DNA. Supramolecular assemblies have been used to bind the major groove of DNA. Such assemblies utilise the cationic charge of the metal ions in the assemblies to interact with the anionic charge on the DNA.

The paper speculates that it may be possible to utilise the metal centres to design cationic DNA binders with large dimensions with polarised H-groups on the outside having the potential to switch genes on and off. Large proof of concept supramolecular cylinders have been produced based on imine-based ligands (see also Hannon M. J. et al. Angew Chem. Int. Ed. 2001, 40, pages 880-884). This was aimed at proving the concept of bridging, synthetically, the size gap between traditional small molecule and larger biomolecule DNA-recognition motifs. An aim of this research was to assist in the investigation of the coding inherent in DNA and how that may be processed or suppressed in biosystems. Binding of such large structures were found to have a dramatic effect on the structure of naked DNA by forming intra-molecular coils. This coiling was speculated as being similar to that found in DNA packaging in the nucleosome. The stated aim of finding assemblies that bind DNA with sequence selectivity is also explicitly stated in the article by Meistermann I et al (PNAS 2002,99, pages 5069-5074).

From this initial work on naked DNA, the authors of the paper speculated that it might be possible to design molecules to achieve sequence specific recognition to allow specific cancer genes to specifically switched on and off, specifically attack viral material or suppressing the excess genetic material found in trisomic disorders such as Down's syndrome.

The supramolecular assemblies used in the prior art were not expected themselves to act as anti-cancer, anti-viral or indeed antibacterial compounds. The limited example used in the prior art is a large molecule by traditional drug standards (2nm length and about lnm diameter). They are also tetracationic and were not expected to cross the cell membrane. The paper by Hannon and Rodger (2002) also states that further work is required to identify compounds that have sequence specificity. There are a large number of DNA binding compounds in the art, such as Hoechst 33258, SYBR Green (tm) and ethidium bromide that are known to bind DNA, but many of which do not have use as anti-cancer agents or antimicrobials. Hence, it was not expected that the limited supramolecular assemblies used in the prior art would be able to cross through cells walls of cells or bacteria, and would be able themselves to be used as anti-cancer, anti-bacterial or anti-viral drugs. Furthermore DNA in cells is considerably more complex, being bound to histones and other proteins to form packaged DNA. The compounds have now also been found to bind RNA. Thus there was a major step in going from such limited work on naked DNA, to applying the technology in cells.

When such compounds were tested by the inventors the compounds were found to be uptaken by cells. Indeed, bacterial cells uptake so much of the compounds that they are stained by the compounds. The compounds have now been found to be toxic to cancer cell lines and to bacterial cells. They have also been shown to inhibit protein synthesis and bind RNA. There are a large number of viruses in many forms, including double stranded and single stranded DNA and RNA viruses. The demonstration of the ability to block protein synthesis by binding DNA and RNA is expected to result in antiviral activity for these compounds.

In a first aspect, the present invention is directed to use of a supramolecular compound derived from a ligand (L) of formula I or II as an antittumour, anti microbial or antiviral agent: Wherein : Each X for formula I may the same or different and may be C or N, wherein when X=N, there is no R group attached to X; R1 to R8 may be independently selected from H, OAlkyl, OAryl, CH2OAlkyl, CH2OAryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, COzH, CO2Alkyl, CO2Aryl, O-, CH20-, CO2-, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2Alkyl, OSO2Aryl, 02Aryl, SO2Me, N (Alkyl) 2 and Alkyne; Z = CH, CAlkyl, CAryl, or CNH2 and may be the same or diffferent Y may be present or not present and may be selected from: R may be selected from H, OAlkyl, OAryl, CH20Alkyl, CH20Aryl, CH2OC (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, C02H, CO2Alkyl, CO2Aryl, O-, CH20-, CO2-, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2Alkyl, OSO2Aryl, SO2Me, N (Alkyl) 2 and Alkyne ; A = NH, S, SO2, O, (CH2) n, CHR, CR2, or NR, where R is as defined above. n = an integer 1,2, 3,4, 5,... 20. Preferably, n = 1 or 2 Or alternatively the ligand may have a general formula II: indicates a 5 membered heterocycle such as imidazole, pyrazole, thiazole, oxazole Where X in formula II may be independently selected and may be C or N, or X can be NH, S, O, in which case the R group is absent. The different X positions can be the same or different.

The remaining groups may be defined as above for Formula I.

The supramolecular compounds may be used as therapeutic agents in general, and epscailly as antitumour, antimicrobial (such as an antibacterial or anti protozoal) or antiviral agents.

In the present invention: Alkyl may be straight or branched (e. g. Methyl, ethyl, 2-propyl, 3-propyl etc. ) which may itself may bear additional functionality (e. g. halides, alcohols, ethers, alkene groups, alkyne groups, amines, and DNA intercalators such as derivatives of ethidium, peptides, peptide nucleic acids (PNAS), and or oligonucleotides).

Aryl may be any aryl unit e. g. Phenyl, 2-, 3-or 4-tolyl, phenol, 2-, 3 or 4-pyridyl and may itself may bear additional functionality (e. g. halides, alcohols, ethers, alkene groups, alkyne groups, amines, and DNA intercalators such as derivatives of ethidium, peptides, peptide nucleic acids (PNAS), and or oligonucleotides).

Alkyne may be any alkyne units e. g. ethyne, trimethylsilylalkyne may itself may bear additional functionality (e. g. halides, alcohols, ethers, alkene groups, alkyne groups, amines, and DNA intercalators such as derivatives of ethidium.

In use, the ligand (L) (defined above) is coordinated to at least two metal ions (M) to produce a supramolecular compound system. Two or more ligands may be coordinated to the metal ions. Each of the ligands may be the same, or alternatively be different to produce a mixed supramolecular compound.

The metal ion may be preferably Fe, Ni, Co, Cu, Ag, Cd, Zn, Ru, Rh, Mn, Ir, Os, Pd, or Pt. Preferably the metal ion is Fe2+, Fe3+, Ni2+, Co2+, Co3+, Cu+, Cul+, Ag+, Cd2+, Zn2+, <BR> <BR> <BR> Ru2+, Ru, Rh, Mn, Mn3+, Ir+, Ir2+, Ir3+, Os2+, Os3+ Pd2+ Pd3+ Pd4+ Pt2+ 4 Two or more different metal ions may be used The system may be represented by the formulae: M2 L2 or M2L3 or M3L3 or more generally Mn Lm where n and m are integers of 2 to 20, preferably 2,3, 4 or 5 and n and m may be the same or different. Most preferable the active agent is M2L3.

The systems may also have an associated anion (s) or solvents (s) or ligand (s).

The stoichiometry of the system produced is dependent on the metal and ligand combination. The system may be homo-ligand or hetero-ligand (i. e. Contain different ligands, for example, [M2 L'L"L"']).

The term indicating that the supramolecular compound"is derived from a ligand (L) of formula I or a ligand of formula II coodinated to at least two metal ions", indicates that the ligand and metal ions have been mixed and have been allowed to coordinate together to form the supramolecular compound.

The supramolecular compound may have a cylindrical structure. Alternatively, they may be modified by means of substituents (including groups such as Y) to form knots, grids, catenanes, boxes, triangles, linear helices, circular helices, capsules, balls or polyhedra.

The inventors have also recognised that the compounds may be used to treat tumours microbial infections, such as bacterial infections or viral infections in e. g. mammals, such as humans.

The compounds may be used in combination with one or more other drugs known to be used for such purposes.

A further aspect of the invention provides the use of a supramolecular compound derived from a ligand (L) of formula I or II, coordinated to at least two metal ions for the manufacture of a medicament to treat a tumour, a microbial infection (such as a bacterial or a protozoal infection), or viral infection: Formula I Wherein : Each X for formula I may the same or different and may be C or N, wherein when X=N, there is no R group attached to X; R1 to R8 may be independently selected from H, OAlkyl, OAryl, CH20Alkyl, CH20Aryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, COzH, CO2Alkyl, CO2Aryl, O-, CH20-, CO2-, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CHzSAryl, OSO2Alkyl, OSO2Aryl, 02Aryl, SO2Me, N (Alkyl) 2 and Alkyne; Z = CH, CAlkyl, CAryl, and or CNH2 and may be the same or different Y may be present or not present and may be selected from: wherein: R may be selected from H, OAlkyl, OAryl, CH2OAlkyl, CH20Aryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, COzH, CO2Alkyl, CO2Aryl, O-, CH20-, CO2-, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2Alkyl, OSO2Aryl, SO2Me, N (Alkyl) 2 and Alkyne; A = NH, S, SO2, O, (CH2)n, CHR, CR2, or NR, where R is as defined above n = 1, 2,3, 4,5,... 20; R may be selected from H, OAlkyl, OAryl, CH20Alkyl, CH2OAryl, CH20C (O) Alkyl, CH20C (O) Aryl, OC (O) Aryl, OC (O) Alkyl, OH, CH20H, CO2H, COaAlkyl, COzAryl, O-, CH20-, CO2-, Alkyl, Aryl, BR, Cl, I, F, CN, NO2, CF3, SAlkyl, SAryl, CH2SAlkyl, CH2SAryl, OSO2Alkyl, OSO2Aryl, SO2Me, N (Alkyl) 2 and Alkyne; Alternatively the ligand may have a genera formula II: indicates a 5 membered heterocycle such as imidazole, pyrazole, thiazole, oxazole Where X in formula II may be independently selected and may be C or N, or X can be NH, S, O, in which case the R group is absent. The different X positions can be the same or different.

The remaining groups may be defined as above for Formula I.

Preferably, the use is for the treatment of cancer.

A further aspect of the invention provides a method of treating tumours, microbial infections (such as bacterial or protozoal infections) or viral infection comprising administering to a patient supramolecular compound derived from a ligand (L) of Formula I or Formula II, as defined above, coordinated to two or more metal ions. The invention also includes within its scope a method of treating cancer by administering such a compound.

Pharmaceutically acceptable salts of the compounds may be used.

The compounds may be used in the form of pharmaceutical compositions.

Pharmaceutical compositions comprising supramolecular compounds, or pharmaceutically acceptable salts thereof, are also provided. They may comprise any pharmaceutically acceptable carrier, adjuvant or vehicle. Pharmaceutically acceptable carriers, adjuvants and vehicles that may be used in the pharmaceutical compositions of this invention include, but are not limited to, ion exchangers, alumina, aluminum stearate, lecithin, serum proteins, such as human serum albumin, buffer substances such as phosphates, glycine, sorbic acid, potassium sorbate, partial glyceride mixtures of saturated vegetable fatty acids, water, salts or electrolytes, such as protamine sulfate, disodium hydrogen phosphate, potassium hydrogen phosphate, sodium chloride, zinc salts, colloidal silica, magnesium trisilicate, polyvinyl pyrrolidone, cellulose-based substances, polyethylene glycol, sodium carboxymethylcellulose, polyacrylates, waxes, polyethylene-polyoxypropylene-block polymers, polyethylene glycol and wool fat.

The pharmaceutical compositions may be administered orally, parenterally, by inhalation spray, topically, rectally, nasally, buccally, vaginally or via an implanted reservoir, preferably oral administration or administration by injection. The pharmaceutical compositions of this invention may contain any conventional non-toxic pharmaceutically-acceptable carriers, adjuvants or vehicles. The term parenteral as used herein includes subcutaneous, intracutaneous, intravenous, intramuscular, intra-articular, intrasynovial, intrasternal, intrathecal, intralesional and intracranial injection or infusion techniques.

The pharmaceutical compositions may be in the form of a sterile injectable preparation, for example, as a sterile injectable aqueous or oleaginous suspension. This suspension may be formulated according to techniques known in the art using suitable dispersing or wetting agents (such as, for example, Tween 80) and suspending agents. The sterile injectable preparation may also be a sterile injectable solution or suspension in a non-toxic parenterally-acceptable diluent or solvent, for example, as a solution in 1,3-butanediol. Among the acceptable vehicles and solvents that may be employed are mannitol, water, Ringer's solution and isotonic sodium chloride solution. In addition, sterile, fixed oils are conventionally employed as a solvent or suspending medium. For this purpose, any bland fixed oil may be employed including synthetic mono-or diglycerides. Fatty acids, such as oleic acid and its glyceride derivatives are useful in the preparation of injectables, as are natural pharmaceutically-acceptable oils, such as olive oil or castor oil, especially in their polyoxyethylated versions. These oil solutions or suspensions may also contain a long-chain alcohol diluent or dispersant such as PH.

Helv or a similar alcohol.

The pharmaceutical compositions may be orally administered in any orally acceptable dosage form including, but not limited to, capsules, tablets, and aqueous suspensions and solutions. In the case of tablets for oral use, carriers which are commonly used include lactose and corn starch. Lubricating agents, such as magnesium stearate, are also typically added. For oral administration in a capsule form, useful diluents include lactose and dried corn starch. When aqueous suspensions are administered orally, the active ingredient is combined with emulsifying and suspending agents. If desired, certain sweetening and/or flavouring and/or coloring agents may be added.

The pharmaceutical compositions may also be administered in the form of suppositories for rectal administration. These compositions can be prepared by mixing a compound of this invention with a suitable non-irritating excipient which is solid at room temperature but liquid at the rectal temperature and therefore will melt in the rectum to release the active components. Such materials include, but are not limited to, cocoa butter, beeswax and polyethylene glycols.

For application topically to the skin, the pharmaceutical composition should be formulated with a suitable ointment containing the active components suspended or dissolved in a carrier. Carriers for topical administration of the compounds of this invention include, but are not limited to, mineral oil, liquid petroleum, white petroleum, propylene glycol, polyoxyethylene polyoxypropylene compound, emulsifying wax and water, Alternatively, the pharmaceutical composition can be formulated with a suitable lotion or cream containing the active compound suspended or dissolved in a carrier. Suitable carriers include, but are not limited to, mineral oil, sorbitan monostearate, polysorbate 60, cetyl esters wax, cetearyl alcohol, 2-octyldodecanol, benzyl alcohol and water. The pharmaceutical compositions of this invention may also be topically applied to the lower intenstinal tract by rectal suppository formulation or in a suitable enema formulation. Topcally-transdermal patches are also included in this invention.

The pharmaceutical compositions of this invention may be administered by nasal aerosol or inhalation. Such compositions are prepared according to techniques well-known in the art of pharmaceutical formulation and may be prepared as solutions in saline, employing benzyl alcohol or other suitable preservatives, absorption promoters to enhance bioavailability, fluorocarbons, and/or other solubilizing or dispersing agents known in the art.

The antimicrobial activity of the compounds also means that the compounds may be used in a disinfectant formualtion. The compounds may be used with one or more additives known in the art for use in disinfectants, such as surfactants (e. g. ionic or non-ionic surfactants), wetting agents, chelating agents etc.. This may be used to disinfect, for example surfaces. Disninfectant comprising a supramolecular compound or a pharmaceutically acceptable salt, derived from a Ligand of Formula I or Formula II, as defined above, coordinated to two or more metal ions.

It is thought that the cationic metal ion assembled supramolecular compounds disclosed are known to have architectures similar to the dimension of protein binding sites that target the major groove in DNA. Hence, the supramolecular compounds recognise the major groove in DNA and induce a structural transformation whereby it warps around the DNA.

The presence of the compound on the DNA may also disrupt the intereaction of the DNA with polymerases such as DNA polymerase and RNA polymerase, resulting in the inhibition of DNA or RNA synthesis and hence indirectly protein synthesis.

Given that, for example, an iron (II) supramolecular compound is helical, it and its analogues exist in two enantimeric forms, and there is cytotoxicity using both the racemic and the two enantiopure forms.

The supramolecular compounds can be cheaply made and, their ability to be modified to give, for example, bi-and poly-metallo-, double-and triple-helicates allows tumours and viruses to be specifically targeted either directly or by tagging onto biomolecules or other targetting agents Preferred ligand for use in the invention may be one or more of any of the compounds, the synthesis of which is shown in the Examples. These include any one of the compounds shown in Figure 1 or Figure 2. These may be used in combination with one or more of the metal ions defined above.

The invention also provides a compound for use in the production of a supramolecular compound, selected from a compound shown any one of the examples and in particular Figure 5. Such compounds may be coordinated to at least two metal ions (e. g. as defined above) to produce a supramolecular compound.

Aspects of the present invention will now be described by way of example only with reference to the following figures : Figure 1 shows alternative compounds for use in the claimed invention Figure 2 shows the ligand used in example 1.

Figure 3. The X-ray crystal structures of the silver (i) complexes of the LR and Ls ligands of example 1 confirming a solid state double helical structure for both complexes (the hydrogen atoms are omitted for clarity). Left hand side Ag2LS22+.

Figure 4 The growth rate of Synechocystis sp. PCC 6803 was assessed in the presence of varying concentrations of the purple supramolecular agent [Fe2 (C2sH2oN4) 3] Cl4 (0-10. lmM). Synechocystis sp. PCC 6803 cultures were grown in 20ml BGII medium contained in 50ml conical flasks and at constant illumination of 30 microEinsteins rri Zsec'. Cell density was measured at 750nm using uninnoculated BG11 media as a blank. The cells stain visibly purple at lO, uM and cell growth is stopped above this concentration.

Figure 5 shows novel compounds for use in the production of supramolecular compounds useful for treating tumours, microbial infections and viral infections.

Production of Supramolecular Compound Coordinated to Metal Ion Supramolecular compounds can be produced using known synthesis pathways. The shape of the compounds formed can be varied by addition of different substituent groups or varying the metal ion and/or ligands used.

Examples Example 1 In the present example, a double helicate structure is produced from a dinuclear silver (i) metal-supramolecular compound.

All starting materials were purchased from Aldrich and used without further purification. NMR spectra (see Structure Figure 2 for the numbering scheme used) were recorded on Bruker DPX300 and DRX500 instruments using standard Bruker software.

ESI mass spectra were recorded on a Micromass Quatro (II) (low resolution triple quandrupole mass spectrometer) at the EPSRC National Mass Spectrometry Service Centre, Swansea. FAB mass spectra were recorded by the Warwick mass spectrometry service on a Mocromass Autospec spectrometer using 30 nitrobenzyl alcohol as matrix.

Microanalyses were conducted on a Leeman Labs DE44 CHN analyser by the University of Warwick Analytical service. Infrared spectra were recorded on a Bruker Vector 220 instrument fitted with an ATR Golden Gate. Circular dichroism spectra were recorded using a Jasco J-715 spectropolarimeter.

Syntheses Ls-[Ag2(C32H22N4)2] [PF6] 2. Pyridine-2carbaldehyde (0.17 cm3, 1.76 mmol) was dissolved in ethanol (3cm3) and heated with a suspension of (S), (-)-1, 1'-binaphthalene-2, 2'-diamine (0.25 g 0. 89 mmol) in ethanol (3cm3) to 79 °C for 18 hours. A suspension of silver (i) acetate (0.15 g, 0.89 mmol) in ethanol (3 cm3) was then added and heating maintained for a further 18 hours. The reaction mixture was then filtered through Celite and ethanolic ammonium hexafluorophosphate added. The yellow precipitate was collected by vacuum filtration (0.35 g, 55%) (Found : C, 51.9 ; H, 3.0 ; N, 7.7 [Ag2 (C32H22N4) 2] [PF6] 212. 5H20 requires C, 52.1 ; H, 3.3 ; N, 7. 6%).'H (300 MHz; CD3CN) : d 8.77 [ [4H, d, J (Himine~Ag) 9.0 Hz, Himine], 8. 14 [4H,td,J(H4py-H3py) 7.7, (H4py-Hspy) 7.7 Hz, H4pyl, 7.92 [4H, d, J (H4py-H3py) 7. 7 Hz, H3pyl, 7.54 [4 H, d, J (H6bi-H7bi) 8. 1 Hz, H6bi], 7.41 [4 H, ddd, J (Hspy-H4ph) 7.7, (H5py-H6py) 4.7 Hz, H5py], 7. 37 [4 H, d, J (H3bi-H4bi) 8. 9 Hz. H3bi], 7.32 [4 H, ddd, j (H7bi-H6bi) 8.1, (H7bi-J8bi) 6.8 Hz, H7bi], 7.15 [4H, ddd, J (H8bi-H9bi) 8.3, (Hsbi-H7bi), 7.07 [4 H, d, J (H4bi-H3bi) 8.9 Hz, H4bi], 6. 78 [4 H, dd J (H9bs-Hsbi) 8.3 Hz, H9bi], 6.72 [4 H, dd, J (H6py-H5py) 4.7 Hz, H6py]. 13C (75.5 MHz; CD3CN): g 162.2 (Cimine) 149.5 (C6py), 147. 8 (C4°), 144.2 (C4o), 139.0 (C4py), 132.5 (4o), 132.2 (C4o), 130.6 (C4bi), 128. 9 (C3py), 128.5 (C6bi), 128.0 (C5py), 127.3 (C8bi), 126.1 (C7bi), 125.7 (C4o), 125.0 (C9bi), 118.6 (C3bi). Positive-ion FAB, mlz 1285 ([Ag2(C32H22N4)2][PF6]+), 1033 ( [Ag2 (C32H22N4) 2+), 571 ([Ag2(C32H22N4)2]+).

Umax/cm-1 3050-2800w, 1615w, 1587m, 1568m, 1439m, 1305m, 1204m, 1006m, 837s, 776m, 750m, 692m, 672m, 651m, 663m, 585s, 556s, 527m, 511m. kmax/nm (MeCN) 229 (e/mol-1dm-3cm-1. 6x105), 279 (1. 0x105), 322 (4. 0x10"), 360 (3. 0x104).

LR-[Ag2 (C32H22N4) 2] [PF6] 2. Preparation as for the (S), (-) silver (i) salt except for the use of the (R), (+)-l, 1'-binaphthalene-2, 2'-diamine spacer group, yield (040 g, 63%) (Found: C, 51.4 ; H, 3.1 ; N, 7.4. [Ag2) C32H22N4) 2] [PF6] 2. 3. 5H20 requires C, 51. 5 ; H, 3.4 ; N, 7. 5%). 1H (300 MHz; CD3CN) : g 8.77 [4 H, d, J (Himine-Ag) 9.0 Hz, Himine], 8.14 [4 H td, J (H4py-H3py) 7. 7, (H4py-H5py) 7.7 Hz, H4pyl, 7. 92 [4 H, d, I (H4py-H3py) 7. 7 Hz, H3py], 7. 54 [4 H, d, J (H, d, J (H6bi-H7bi) 8.1 Hz, H6bi], 7.41 [4 H, ddd, J (Hspy-H4py) 7.7, (H5py-H6py) 4.7 Hz, H5py], 7. 37 [4 H, d, J (H3bi-H4bi) 8. 9 Hz, H3bi], 7.32 [4 H, ddd, J(H7bi-H6bi) 8.1, (H7bi-Hsbi) 6. 8 Hz, H7bi], 7.15 [4 H, ddd, J(H78bi-H9bi) 8.3, (H8bi-Hbi) 6.8 Hz, Hsb.], 7.07 [4 H d, J (H4bi-H3bi) 8. 9 Hz, H4bi], 6.78 [4H, dd, J(H9bi-H8bi) 8. 3 Hz, H9bi], 6.72 [4H, dd, J (H6py-H5py) 4.7 Hz, H6py]. 13C (75.5 MHz; CD3CN): g 162.2 (Cimine), 149.5 (C6py), 147.8 (C4o), 144.2 (C4o), 139.0 (C4py), 132.5 (C40), 132.2 (C40), 130.6 (C4bi), 128.9 (C3py), 128. 5 (C6bi), 128. 0 (C5py), 127.3 (C8bi), 126.1 (C7bi), 125.7 (C4O), 125. 0 (Cab.), 118.6 (C3bi).

Positive-ion FAB, m/z 1285 ([Ag2(C32H22N4)2] [PF6] +, 93%), 1140 ([Ag2(C32H22N4)2]+, 90%), 571 ([Ag2(C32H22N4)]+, 53%). Positive-ion ESI, mlz 1285 ([Ag2(C32H22N4)2][PF6]+), 1033 ([Ag2(C32H22N4)2]+), 571 ([Ag2(C32H22N4)2]2+). vmax/cm-1 3050-2800w, 1615w, 1567m, 1568w, 1504m, 1439m, 1304m, 1204m, 1005m, 831s, 777s, 757s, 739s, 693m, 673m, 651m, 651m, 632m, 621w, 555s, 523w, 509w. kmax/nm (MeCN) 229 (e/mol-1dm-3 cm-1 1.6 x 105), 279 (1.0 x 105), 322 (4.0 x 104), 360 (3.0 x 104).

X-Ray Crystallography Suitable crystals of Ls- ( [Ag2 (C32H22N4) 2] [PF6] 2 from nitromethane-diethyl ether.

Crystallographic data are collected in Table 1. Data were measured on a Siemens SMART27 three-circle system with CCD area detector using the oil-mounting method at 180 (2) K (maintained with the Oxford Cryosystems Cryostream Cooler). 28 Absorption correction by u-scan. The structures were solved by direct methods using SHELXS29 (TREF). CCDC reference numbers 166445 and 166446.

Table 1 Crystallographic data and structural refinements for the LR and LS silver(I) double helicates Complex LR silver(I) helix Ls silver (1) helix Empirical formula C65. 50H48.50Ag2F12N9,50O3P2 C147.50H107Ag4F24N16P4 Formula weight 1522.32 3114.85 Temerature/K 180 (2) 180 (2) Crystal System P3, P2, Space group Trigonal Monoclinic al A 14. 38840 (10) 13.1740 (2) bl Å 14 38840 (10) 32.1983 (2) cl Å 27.22160 (10) 17.9687 (3) al'90 90 ßl° 90 108.6280 (17), 2 01° 120 90 V/Å3, Z 4880.55 (5), 3 7222.67 (17), 2 µ/mm-1 0.739 0.644 Crystal size/mm 0, 4 x 0.4 x 0.2 0. 36 x 0.36 x 0.2 Reflections collected 31885 46496 Independent reflections 15474 (Rinl=0. 0266) 31159 (Ri. t=0. 0766) Data/restraints/parameters 15474/1/869 31159/1/1706 Goodness-of-flt on F¢ 0. 958 0. 900 Final R indices [I>2r(I)] R1 = 0. 370, wR2 = 0.0749 R I = 0. 0662, wR2 = 0. 1182 R indices (all data) Rl = 0.0593, wR2 = 0. 0820 Ru = 0. 2412, wR2 = 0. 1700 Largest difference peak, hole/ e Å-3 0.506, -0. 402 0. 566,-0. 477 Absolute structure parameter-0. 010 (14) 0. 01 (2) Crystallographic investigations. X-Ray quality crystals of both complexes were obtained from nitromethane solutions by slow diffusion of diethyl ether for the LR complex and benzene for the L'complex. The X-ray structural analyses confirm that the solid state structures of the two complexes are dinuclear double helicates. The crystal structures demonstrate that, as anticipated, the chiral twisting of the binaphthalene can be used to control the helicity of the array. The coordination of two LR ligands around two 4pytetrahedral ions results in the formation of a P (right-handed) 4 double helix and that the coordination of two Ls ligands around two silver (i) tetrahedral ions similarly result in the formation of an M (left-handed) double helix (Fig. 3). (For the L'enantiomer, two very similar but crystallographically distinct cations are present in the solid state structure).

Each silver) centre is four-coordinate pseudo-tetrahedral, bound to two pyridylimine units, each of which is approximately planar (pyridyl-imine torsion angles in the range 3-11°). The naphthalene units are twisted with respect to the imine group (torsion angles in the range 38-44°) and a more dramatic twisting is observed between the naphthalene rings which are almost perpendicular to each other (torsion angles in the range 70-78°). The combination of these twistings gives rise to the formation of the double helical structure, the chirality of the helical arrays being prescribed by the chiral twist inherent in the binaphthalene unit. The two silver (I) centres within the helical dications are separated by 3.61-3. 78 A. Within the helical arrays each pyridyl is stacked on top of a naphthalene unit. Such extensive face-face o-stacking interactions are also observed in polypyridyl helicates and presumably contribute to the stabilisation of the structure. Although the conditions used to prepare the helicates were quite vigorous, the chirality of the spacer groups and in consequence the ligands is preserved (steric hindrance in the binaphthalene units result in a relatively high activation energy for inversion of configuration).

Further Examples Materials All starting materials were purchased from Aldrich and BDH, the compounds were used without further purification.

Measurements NMR spectra were recorded on Bruker DPX 300 and ACP 400 instruments using standard Bruker software. FAB mass spectra were recorded by the Warwick mass spectrometry service on a Micromass Autospec spectrometer using 3-nitrobenzyl alcohol as matrix. Microanalyses were conducted on a Leeman Labs CE44 CHN analyser by the University of Warwick Analytical service. X-ray crystallography data were measured on a Siemens SMART three-circle system with CCD area detector using the Oxford Cryosystems Cryostream Cooler. Infrared spectra were recorded on a Bruker Vector 220 instrument fitted with an ATR Golden Gate.

Syntheses 6-Hydroxymethylpyridine-2-carboxaldehyde 2,6-Pyridinedimethanol (2 g, 0.014 mol) in isopropanol (70 cm3) was heated to gentle reflux. Then activated manganese (IV) oxide (< 5 micron) (1.25 g, 0.014 mol) was added portion wise over 1 hour. Gentle reflux was continued for 6 hours. After this time the black solution was filtered hot through Celite and the residue washed with hot isopropanol (30 cm3). The solvent was removed in vacuo to yield a pale yellow solid.

The solid was subjected to flash chromatography on silica gel 60, loaded in DCM and eluted with 5% methanol : DCM. Fractions with Rf=0. 55 (TLC run with 5% methanol : DCM) were collected to yield a yellow oil which crystallised in the fridge to a pale yellow solid. The product was dried under high vacuum over P205 to constant weight (0.64g, 33%) Microanalysis: found C, 60.9 ; H, 5.3 ; N, 10.1. Calculated from C7H7NO2 : C, 61.3 ; H, 5.1 ; N, 10. 2% Positive ion Fast Atom Bombardment (FAB): m/z 137 (M+), 120 (M+-OH)'H NMR (CDCI3, 400 MHz, 298K) : # 10.06 (1H, s, CHO), 7.89 (2H, 2d, J=7.5 Hz, H4+H5), 7.52 (1H, t, J=7.3 Hz, H4), 4. 88 (2H, s, CH2), 3.81 (H, br s, OH) ppm 13C NMR (CDCI3, 400 MHz, 298K): d 192.9 (Cald.), 148.0 (C2), 138.1 (C4), 136.5 (C3), 128.4 (C5), 64.9 (C6), 53.4 (CH2) ppm L3 (C27H24N4O2) 6-Hydroxymethylpyridine-2-carboxaldehyde (0.137 g, 1.0 mmol) in ethanol (25 cm3) was added dropwise to an ethanolic solution of 4, 4' methylene dianiline (0.099 g in 25 ml, 0.5 mmol) over 30 min. The resulting yellow solution was left stirred at room temperature for 24 hours. A pale cream solid precipitated and was collected by vacuum filtration. The product was dried under vacuum over P2O5 to constant weight (0.156 g, 72 %) Positive ion EI : m/z 435 (M+, 95%), 418 (M+-OH, 15%), 401 (M+-2 OH, 20%), 404 (M+-CH20H, 15%) 'H NMR (CDCl3, 400 MHz, 298K): d 8.73 (1H, s, Him), 8. 19 (1H, d, J=7. 8 Hz, H3), 7.85 (1H, t, J=7. 8 Hz, H4), 7.33 (1H, d, J=7.8 Hz, H5), 7.26 (4H, s, Hph), 4.83 (2H, s, CHO), 4.06 (1H, s, CH2spacer) 3. 80 (1H, br s, OH) ppm [Cu2L'2] (PF6) 2To a stirred solution of L3 (0.043 g, 0.1 mmol) in dry methanol (5 cm3) was added [Cu (MeCN) 4] [PF6] (0.037 g, 0.1 mmol) dissolved also in dry methanol (5 ml) under nitrogen. The red-brown solution was stirred at room temperature under nitrogen for 16 hours. The red-brown solid was subsequently filtered under vacuum and washed with diethyl ether (1 cm3). The product was dried under vacuum over P205 to constant weight. (0.045 g, 70%) Positive-ion FAB: m/z 1143 ([Cu2(L3)2(PF6)]+), 1000 ([Cu2 (L3) 2] +tH NMR (CD3CN, 400 MHz, 298K): d 9.24 (1H, s, H'), 8.25 (1H, t, J=7.8 Hz, H4), 8.02 (1H, d, J=7.9 Hz, H3), 7.91 (1H, d, J=7.9 Hz, H'), 7. 36 (2H, d, J=8.0 Hz, Hph), 7.18 (2H, d, J=8.2 Hz, Hop), 4.32 (2H, bd, CH20H), 3.87 (1H, s, CH2spacer), 3.47 (1H, bs, OH) ppm 'H NMR (CD3CN, 500 MHz, 233K): d 9.37 (2H, s, H'box) 9.30 (7H, s, H'hel), 8.23 (9H, m, H4 box, H4 hel), 8. 00 (9H, d, J=7.8 Hz, H3 hel,. H3 box), 7. 88 (7H, d, J=7.8 Hz, H'hel), 7.84 (2H, d, J=7.8 Hz, H'box), 7. 43 (4H, d, J=8. 2 Hz, HPh box), 7. 33 (14H, d, J=8.2 Hz, HPh hel) 7.23 (4H, d, J=8.2 Hz, HPh box), 7.16 (14H, d, J=8. 2 Hz, HPh hel), 4.29 (7H, dd, J=15. 9,6. 2 Hz, CH OH hel), 4.22 (2H, dd, J=15. 9,5. 6 Hz, CL OH box), 4.11 (7H, dd, J=16. 2,6. 2 Hz, CL OH hel), 4.07 (2H, dd, J=16. 2,6. 2 Hz, CH OH box), 3.90 (1H, d, J= 12.8 Hz CH2spacer box), 3.81 (8H, s, CH2spacer hel, CH2spacer box) 3.75 (9H, m, OH hel, OH box) ppm. Imax/nm (MeCN) 510 (e/mol-1dm-3cm-1 2.6x104) MLCT nmax/cm-1 3500-3000w, 2357m, 1596m, 1501m, 1463m, 1269m, 1200m, 1161,1079m, 1012m, 910m, 828s, 789m, 737m, 648m, 612m, 603m.

[Cu2L42] (PF6) 2 6-Hydroxymethylpyridine-2-carboxaldehyde (0. 137 g, 1.0 mmol) was dissolved in dry methanol (15 ml) with 4, 4'methylene bis 2,6 diethyl aniline (0.155 g, 0.5 mmol).

The pale yellow solution was left stirring at room temperature under nitrogen for 30 min. Then [Cu (MeCN) 4] [PF6] (0. 018 g, 0.5 mmol) dissolved in dry methanol (5 ml) was added to the solution under a blanket of nitrogen. The solution, which quickly becomes red-brown in colour, was stirred at room temperature under nitrogen for 15 hours. The red-brown solid which precipitated was filtered off under vacuum and washed with diethyl ether (2 cm3). The product was dried under vacuum over P20s to constant weight. (0.27 g, 36%) Positive-ion FAB: m/z 1369 ([Cu2(L4)2(PF6)]+), 1224 ( [Cu2 (L) 2]) 'H NMR (CD2CI2, 400 MHz, 298K): d 8.50 (1H, s, Him), 8.26 (1H, t, J=7.8 Hz, H4), 8. 12 (1H, d, J=7. 8 Hz, H3), 7.89 (1H, d, J=7.8 Hz, H'), 7.14 (1H, s, HPh), 6. 58 (1H, s, HPh), 4.35 (1H, dd, J=14.1, 4.1 Hz CHOH), 3.95 (1H, br d, J=13.8 Hz CHO), 3.92 (1H, s, CH2spacer), 3.07 (1H, br s, OH) 2.59 (2H, m, CH7Me), 1.91 (2H, m, CH2Me), 1.03 (3H, t, J=7.4 Hz, Me), 0.64 (3H, t, J=7.3 Hz, Me) ppm.

Imax/nm (MeCN) 466 (e/mol-1dm-3cm-1 3x104) MLCT nmax/cm-1 3500-3000w, 2962m, 1615m, 1583m, 1461m, 1428m, 1399m, 1339m, 1316m, 1194m, 1140m, 1083m, 1003m, 979m, 920m, 880m, 844s, 789m, 735m, 648m, 607m The chloride salt [Cu2L42] Ck was prepared in an analogous manner from copper (I) chloride L [Ru2L3]4+ Ru (DMSO) 4Cl2 (0. 485 g, 1 mmol) and L (0.564 g, 0.67 mmol) were added to 15 mL of ethylene glycol, purged for 12 h with dinitrogen and then heated at reflux for 10 days under dinitrogen. The orange mixture was cooled to room temperature and poured into a concentrated methanolic solution of NH4PF6. The orange-red precipitate was collected by filtration and dried over P40lo. This crude product was dissolved in acetonitrile and loaded onto a neutral alumina column and eluted with a mobile phase of CH3CN : Hz0 : saturated aqueous KNO3 20: 1: 1. The triple helical cylinder [Ru2Ls] was eluted from the column (second band) as an orange band from which an orange solid (0.026g) precipitated on concentrating.

Positive ion ESI-MS (CH3CN/MeOH) : m/z = 333.2 [Ru2L3] 4+.

'H NMR (CD3CN, 298 K, 300MHz) d = 8.77 (1H, s, Him), 8.48 (1H, d, J = 7. 2 Hz, H3), 8. 3 (1H, td, J= 7.7, 1. 5Hz, H4), 7.73, (1H, td, J= 7.5, 4.9 Hz, 1.3 Hz, Hs), 7.66 (1H, d, J= 4.9 Hz, H6), 6. 97 (2H, d, J= 8. 5, Hph), 5.74 (2H, d, J= 8.7, Hph), 4.03 (1H, s, CH2 spacer) ppm PREPARATION OF LIGAND NH2-L Scheme: Ligand NH2-L 4, 4'-diaminodiphenylamine sulphate 85% (0.5 g, 1.43 mmol) was dissolved in water (50 mL) and mixed with pyridine-2-carboxaldehyde (0.27 mL, 2.86 mmol). The solution was stirred for 1 hour and the green-yellow precipitate collected by filtration.

The resulting solid was finally washed with water (10 mL) and dried in vacuo.

NH2-L. Yield 0.23 g. , 43 %; +ve FAB MS: m/z= 378 (M+1) ; 'H NMR (DMSO-d6, ppm): d 6.00 (s, 1H), 7.14 (d, 4H, J= 8.3 Hz), 7.34 (m, 6H), 7.80 (t, 4H, J= 8. 3 Hz), 8. 20 (d, 2H, J=7.5 Hz); 8.66 (s, 2H), 8. 71 (d, 2H, J=4.5 Hz).

PREPARATION OF COMPLEX [Fe2 (NH2-L) 3]Cl4 4,4'-diaminodiphenylamine sulphate 85% (0.5 g, 1.43 mmol) was dissolved in methanol (50 mL) and treated with excess of Na2C03 The suspension was filtered to remove the Na2CO3 excess and to the solution pyridine-2-carboxaldehyde (0.27 mL, 2.85 mmol) and FeCl2x4H20 (0.27 g, 2.85 mmol) were added. The resulting mixture was heated at reflux for 3 hours with a Dean-Stark trap and concentrated to half volume. The addition of diethyl-ether (10 mL) precipitated a solid which was collected by filtration and dried in vacuo.

[Fe2 (NH2-L) 3] Cl4. Yield (0.31 g. 47%); +ve FABMS: m/z = 1313 {Fe2 (NH2-L) 3Cl2} ;'H NMR (DMSO-d6, ppm): d 5.54 (d, 4H, 7.5 Hz), 6.69 (d, 4H, 7,5 Hz), 7.39 (d, 2H, J= 5.6 Hz), 7.60 (dd, 2H, J= 7.5, 5.6 Hz), 8.20 (t, 2H, 7. 8 Hz), 8.43 (d, 2H, 7.5 Hz), 9.07 (s, 1H).

The resolution of the supramolecular iron triple-helicate enantiomers was performed by chromatography using cellulose (-20 micron; Aldrich) as stationary phase and an aqueous 20mM NaCI solution as mobile phase. The solutions obtained at the beginning and at the end of the separation show opposite CD-spectra and correspond to the P and M enantiomers respectively.

Preparation of L : To a stirred solution of pyrazinecarboxaldehyde (0.237g, 2.2 mmol) in ethanol (10 ml) at room temperature was added dropwise an ethanolic solution of bis (4-aminophenyl) methane (0.218g, 1.1 mmol). After the addition was complete, the reaction mixture was stirred at room temperature for 24 hours. The resultant precipitate was filtered off, washed with ethanol and dried in vacuo under P4010 to afford 0.27g (71%) of yellow solid.

Mass spectrum (FAB): m/z = 379 [M+H] + Elemental analysis calculated (%) for C23Hz8N6 : C: 73.0, H: 4. 8, N: 22.2 ; found: C: 72.7, H: 4. 8, N: 22.0.

'H NMR (300MHz, CDC13, 298 K): d = 9.41 (1H, s, H'), 8.63 (3H, m, H3, H5, H6), 7.27 (4H, s, HPh), 4.05 (1H, s, CHz).

IR: n = 2930 (s), 1626 (m), 1589 (m), 1574 (s), 1518 (m), 1497 (s), 1467 (m), 1408 (vs), 1345 (m), 1289 (m), 1196 (w), 1166 (s), 1147 (s), 1048 (s), 1012 (vs), 953 (s), 943 (m), 869 (vs), 859 (vs), 816 (m), 787 (vs), 755 (s) 670 (s) cm-'.

Coordination of L to silver (I) : Care was taken to exclude light during the following procedure. L (0. Olg, 0. 03mmol) in chloroform and silver (I) hexafluorophosphate (0.0075g, 0.03 mmol) in methanol were stirred for 6 hours. The yellow precipitate was collected by vacuum filtration, washed with methanol and dried in vacuo under P4Olo (0. Olg, 26%). X-ray quality, pale yellow crystals were obtained by slow diffusion of diethyl ether into a solution of the complex in acetonitrile.

Mass spectrum (FAB) m/z = 1117 [Ag2L2 (PF6) ], 972 [Ag2L2] Elemental analysis calculated (%) for [Ag2 (C23HlsN6) 2] (PF6) 2-0. 5H20: C: 43.4, H: 2.9, N: 13.2 ; found: C: 43.3, H: 2.9, N: 13.0.

IR: n = 2990 (w), 1626 (w), 1582 (w), 1406 (m), 1375 (w), 1317 (w), 1204 (w), 1166 (m), 1153 (m), 1107 (w), 1055 (m), 1030 (m), 970 (w), 837 (vs), 784 (m), 756 (m), 680 (w) cm-'.

Coordination of L to copper (I) : L (0.017g, 0. 048mmol) was dissolved in chloroform and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] BF4 (0. 018g, 0.048 mmol) in methanol was added to give a dark brown solution. The solution was heated under reflux overnight and then cooled to room temperature. A dark brown solid precipitated from the solution and was collected by vacuum filtration, washed with methanol and dried in vacuo under P4010 (0.03g, 59%). X-ray quality, dark brown crystals were obtained by slow diffusion of diethyl ether into a solution of the complex in nitromethane.

Mass spectrum (FAB) m/z = 971 [Cu2L2 (BF4) ], 884 [Cu2L2] Elemental analysis calculated (%) for [Cu2 (C23HisN6) 2] (BF4) 2-CH30H : C: 51.8, H: 3.7, N: 15.4 ; found: C: 51.7, H: 3.1, N: 15.3.

1H NMR (300MHz, CD3CN, 298 K): d = 9.28 (1H, s, H'), 9.17 (1H, s, H3), 8.93 (1H, br, H5/6), 8. 56 (1H, br, H5/6), 7. 37 (2H, d, J= 8. 5 Hz, Ph), 7.24 (2H, d, J= 8. 3 Hz, HPh), 3.92 (1H, s, CH2).

IR: n = 3029 (w), 2916 (w), 1610 (w), 1505 (m), 1471 (m), 1422 (s), 1404 (s), 1361 (m), 1308 (m), 1203 (m), 1169 (s), 1157 (s), 1095 (s), 1057 (vs), 955 (m), 867 (m), 841 (m), 826 (m), 785 (s), 753 (m), 677 (m) cm-'.

Coordination of L to iron (II) : L (0.025g, 0. 07mmol) and iron (II) tetrafluoroborate (0.016g, 0.046 mmol) in a mixture chloroform-methanol (1: 1) were stirred for 24 hours at room temperature. The violet precipitate was collected by vacuum filtration, washed with methanol and dried in vacuo under P401o (0. 04g, 54%).

Mass spectrum (FAB) m/z = 1505 [Fe2L3 (BF4) 3], 1420 [Fe2L3 (BF4) 2], 1352 [Fe2L3 (BF5)], 1333 [Fe2L3 (BF4)], 1265 [Fe2L3].

Elemental analysis calculated (%) for [Fe2 (C23H, sN6) 3] (BF4) 4-3H20 : C: 50.3, H: 3.7, N: 15.3 ; found : C: 50.4, H: 3.8, N: 15.2.

IR : n = 2987 (w), 1607 (w), 1501 (m), 1468 (w), 1411 (m), 1400 (m), 1352 (w), 1294 (w), 1207 (m), 1170 (m), 1056 (vs), 915 (w), 842 (m), 784 (m), 758 (m), 684 (m) cm-1.

Preparation of L : To a solution of sodium ethoxide prepared from 1.3 g of sodium and 30 ml of absolute ethanol is added a solution of 5-hydroxi-2-methylpyridine (5. 0 g, 0.05 mol) in 15 ml of ethanol followed by 6.86 ml (0.05 mol) of 2-benzoethyl bromide. The mixture is refluxed for three hours, poured into 150 ml of water and extracted with ether. The extract is dried and then treated with ethereal hydrogen chloride. The hydrochloride salt is dissolved in water and then the aqueous solution is washed with ether, basified and extracted with ether. The dried extract is evaporated to give 5-ethylbenzyloxy-2-methylpyridine as a yellow oil. (3.2g, 0. 015 mol).

'H NMR (300MHz, CDC13, 298 K): d = 8.15 (1H, d, J= 2.6 Hz, H6), 7.3 (5H, m, HPh), 7.04 (2H, m, H3, H4), 4.14 (2H, t, J= 7.1, 6.9 Hz, CHa), 3.05 (2H, t, J= 6.9, 6.9 Hz, CH2).

5-ethylbenzyloxy-2-methylpyridine (3.2g, 0.015 mol), hydrogen peroxide 30% (3.5 ml, 0.03 mol) and acetic acid (30 ml) were heated to 80°C for 2.5 hours. The solution was stirred at room temperature for further 24 hours and concentrated under reduced pressure. The resulting yellow oil is neutralized with sodium carbonate. Chloroform is added and the Na2CO3 and NaOAc were removed by filtration. The dried filtrate is evaporated to give 5-ethylbenzyloxy-2-methylpyridine-N-oxide (5.2g, 0.02 mol).

'H NMR (300MHz, CDC13, 298 K): d = 8.22 (1H, d, J= 2.5 Hz, H6), 7.3 (5H, m, HPh), 6.93 (1H, d, J= 2.5 Hz, H3), 6.90 (1H, d, J= 2.5 Hz, H4), 4.14 (2H, t, J= 6.8, 6.7 Hz, CH2), 3.04 (2H, t, J= 6.8, 6.8 Hz, CH2).

To 10 ml of acetic anhydride stirred at 135°C is added slowly 5.2 g (0.02 mol) of the above N-oxide. The solution is stirred at this temperature for 30 minutes and then poured into 100 ml of ice-water. After stirring the mixture for 2 hours it is extracted with a mixture of ethyl acetate and ether. The extract is washed with water, dried and evaporated to dryness. The residue is passed through an alumina column with ether as the eluent. Evaporation of the first fraction yields 2-acetoxymethyl-5-ethylbenzyloxypyridine (1. Sg, 0.006 mol).

IH NMR (300MHz, CDC13, 298 K): d = 8. 24 (1H, d, J= 2. 8 Hz, H6), 7.3 (5H, m, HPh), 7.14 (1H, d, J= 2.2 Hz, H3), 7.12 (1H, d, J= 2. 8 Hz, H4), 5.1 (2H, s, CH2), 4.17 (2H, t, J= 7.2, 6.9 Hz, CH2), 3.07 (2H, t, J= 6.9, 6.9 Hz, CH2), 2.08 (3H, s, CHs).

A solution of 1.5 g (0.006 mol) of the above acetoxymethyl compound in 12 ml ethanol and 3 ml water is treated with 0.41 g NaOH and refluxed for four hours. The solution is evaporated and the residue is taken up in a mixture of ethyl acetate and ether. This solution is washed with water, dried and evaporated to dryness, given 5-ethylbenzyloxy-2-hydroxymethylpyridine as a yellow oil (1.241g, 0.005 mol).

'H NMR (300MHz, CDC13, 298 K): d = 8.18 (1H, d, J= 1.3 Hz, H6), 7.3 (5H, m, HP"), 7.13 (2H, m, H3, H4), 4.64 (2H, s, CH2), 4.17 (2H, t, J= 7.1, 6.9 Hz, CH2), 3.07 (2H, t, J = 7. 1,6. 9 Hz, CH2).

A well-stirred mixture of 1.241 g (0.005 mol) of the above hydroxymethyl compound and 11.7 g of activated manganese dioxide in 60 ml of chloroform is refluxed for 5 minutes. The manganese dioxide is filtered and the solvent evaporated to give a yellow oil, which is purified on silica column with ether-hexan (7: 3) as eluent. The evaporation of the second fraction give 5-ethylbenzyloxy-2-pyridinecarboxaldehyde (1. Og, 0.4 mmol); Mass spectrum (FAB): m/z = 228 [M+H]+; 1H NMR (300MHz, CDC13, 298 K) : d = 9.92 (1H, s, Hald), 8. 36 (1H, d, J= 2.6 Hz, H3), 7. 88 (1H, d, J = 8. 6 Hz, H4), 7.25 (6H, m, 5HPh + H6), 4.25 (2H, t, J= 6.9, 6.7 Hz, CH2), 3.1 (2H, t, J= 6.9, 6.7 Hz, CH2), To a stirred solution of 5-ethylbenzyloxy-2-pyridinecarboxaldehyde (l. Og, 0. 4mmol) in ethanol (10 ml) at room temperature was added dropwise an ethanolic solution of bis (4-aminophenyl) methane (0.435g, 0.2 mmol). After the addition was complete, the reaction mixture was stirred at room temperature for 2 hours. The resultant precipitate was filtered off, washed with ethanol and dried in vacuo under P4010 to afford 0.86g (70%) of white solid.

Mass spectrum (FAB): m/z = 617 [M+Hl Elemental analysis calculated (%) for C41H36N402'0. 75H20 : C: 78.1, H: 6.0, N: 8.9 ; found: C: 77.9, H: 5.9, N: 8. 9.

1H NMR (300MHz, CDCIs, 298 K): a = 8. 57 (1H, s, H'), 8. 44 (1H, s, H6), 8.15 (1H, d, J = 8. 6 Hz, H3), 7.26 (1OH, m, 5HPh, 4HPh, H4), 4.30 (2H, t, J= 6.9, 6.7 Hz, CH2), 3.17 (2H, t, J= 6. 9,6. 7 Hz, CH2).

Coordination of L to iron (II0 : L (0. lg, 0. 15mmol) and iron (II) chloride (0.02g, 0.1 mmol) in a mixture chloroform-methanol (1: 1) were refluxed for 3 hours. The resulting red-purple solution was cooled and treated with saturated solution of ammonium triflate. The red-purple precipitate was collected by vacuum filtration, washed with methanol and dried in vacuo under P4O10 (0.8g, 60%). X-ray quality, red-purple crystals were obtained by slow diffusion in a H-tube of a methanolic solution of ammonium triflate into methanolic solution of the chloride complex.

Mass spectrum (FAB) m/z = 2409 [Fe2L3 (CF3SO3) 3], 2259 [Fe2L3 (CF3SO3) 2], 2111 [Fe2L3 (CF3SO3)].

Positive-ion ESI (MeCN) : milz = 1130 ([Fe2L3(CF3SO3)]2+), 703 ([Fe2L3(CF3SO3)]3+), 490 ([Fe2L3]4+).

'H NMR (500MHz, CD3CN, 298 K): d = 8.85 (1H, s, H'), 8.45 (1H, d, = 8.5 Hz, H3), 7.79 (1H, dd, J= 6.0, 2.5 Hz, H4), 7.26 (5H, m, 5HPh), 6.97 (1H, s, H6), 6.90 (2H, br, HPh), 5. 48 (2H, br, HPh), 4.30 (2H, td, J = 9.0, 7.0, 3.0 Hz, CH2), 4.00 (2H, s, CHa), 3.06 (2H, t, J= 7.0 Hz, CH2).

Preparation of L" To an ethanol solution (15 mL) of 2-formyl-5-hydroxymethylpyridine (0.274 g, 2 mmol) was added very slowly an ethanol (10 mL) solution of hydrazine monohydrate (0.5 g, 1 mmol). The reaction mixture was stirred at RT for 6 h and the resulting pale yellow precipitate were filtered off, washed with ethanol and dried overnight under P4010 to afford 0.21 g, yield 77,7 %.

Mass spectrum (FAB): m/z 271 [M+H] + 'H NMR (300 MHz, CDC13, 298 K): d = 8. 13 (2H, s, Him), 7.65 (1H, d, J= 7.71 Hz H4), 7.40 (1H, d, J = 7.71 Hz, H3), 4.21 (2H, s, OH), 3.82 (1H, s, H6? ??), 3.20 (2H, d, H7,8) Coordination of L"to Fe (II).

Ligand L"was dissolved in methanol and to this solution was added very quickly the Fe (Cl04) 2 4H20. Immediately, the purple precipitate formed was collected by vacuum filtration and dried over P401o.

X-ray quality, purple-black crystals were obtained by slow diffusion of diethyl ether into a solution of the complex in acetonitrile.

Mass spectrum (FAB): m/z 1221 [Fe2L3(PF6)3]+, 1121 [Fe2L3 (PF6) 2] 2+ 1022 [Fe2L3(PF6)]3+ 'H NMR (300 MHz, CD3CN, 298 K): d = 8.84 (1H, s, Him), 8.36 (1H, d, J= 8. 1 Hz, H4), 8. 23 (1H, d, J= 8.1 Hz, H3), 7.26 (1H, s, H6), 4.66 (2H, m), 3.71 (1H, m) Preparation of LMe : To a stirred solution of 2-quinolinecarboxaldehyde (0.068g, 0.43 mmol) in ethanol (30 ml) at room temperature was added dropwise an ethanolic solution of 4, 4'-methylenbis (2,6-dimethylaniline) (0.0541g, 0.215 mmol). After the addition was complete, the reaction mixture was stirred at room temperature for 24 hours. The resultant precipitate was filtered off, washed with ethanol and dried in vacuo under P4010 to afford 0.094g (82%) of yellow solid.

Mass spectrum (FAB) : m/z= 533 [M+H]+ Elemental analysis calculated (%) for C37H32N4-0. 25H20 : C: 82.7, H: 6.1, N: 10.4 ; found : C: 82. 7, H: 6.1, N: 10.3.

'H NMR (300MHz, CDC13,298 K) : d = 8.56 (1H, s, H'), 8. 43 (1H, d, J= 8.5 Hz, H3), 8. 30 (1H, d, J= 8.6 Hz, H4), 8.20 (1H, d, J= 7.7 Hz, H9), 7.90 (1H, d, J= 8.1 Hz, H6), 7.78 (1H, t, J= 7.1 Hz, H8), 7.63 (1H, t, J= 7.3 Hz, H7), 6.97 (2H, s, H"), 3.88 (1H, s, CH2), 2.19 (3H, s, CH3).

IR: õ = 2901 (w), 1634 (s), 1595 (m), 1559 (w), 1502 (m), 1476 (m), 1427 (m), 1378 (m), 1306 (w), 1233 (w), 1200 (s), 1136 (m), 1110 (m), 1020 (w), 972 (w), 894 (m), 880 (w), 852 (w), 828 (vs), 770 (m), 745 (s), 727 (m), 688 (w) cm-1.

Coordination of Lm'to silver (l) : Care was taken to exclude light during the following procedure. LMe (0.02g, 0.04 mmol) in chloroform and silver (I) hexafluorophosphate (0.01 g, 0.04 mmol) in methanol were stirred at room temperature for 4 hours. The orange precipitate was collected by vacuum filtration, washed with chloroform and dried in vacuo under P4010 (0.04g, 75%). X-ray quality, orange crystals were obtained by slow diffusion of diethyl ether into a solution of the complex in nitromethane.

Mass spectrum (FAB) m/z = 2210 [Ag3 (LMe) 3 (PF6) 2], 2065 [Ag3 (LMe) 3 (PF6)], 1550 [Ag3(LMe)3(PF6)(PF5)], 1424 [Ag2 (LMe) 2 (PF6)], 1279 [Ag2(LMe)2], 1172 [Ag (LMe) 2], 766 [Ag2(LMe)(H2O)], 746 [Ag2 (LMe)], 638 [Ag (LMe)].

Elemental analysis calculated (%) for [Ag3 (C37H32H4)3] (PF6) 3 : C: 56.6, H: 4.1, N: 7.1 ; found: C: 59.9, H: 4.5, N: 6.2.

'H NMR (300MHz, CD3CN, 298 K): a = 8. 75 (1H, d, J= 8.4 Hz, H9), 8. 72 (1H, s, Hi), 7.95 (2H, dd, J = 8.2, 7.1 Hz, H3, H4), 7.94 (1H, d, J = 8.2 Hz, H6), 7.69 (1H, ddd, J= 8.1, 6.9, 1.1 Hz, H7/8), 7.60 (1H, ddd, J= 8.4, 6.9, 1. 1 Hz, H7/8), 6. 88 (2H, s, H10), 3.88 (1H, s, CH2), 1.97 (3H, s, CH3).

'H NMR (500MHz, CD2CI2, 283 K): ä = 8. 76 (3H, m, H'helix and trimer, H9 trimer), 8. 70 (1H, d, J= 6.5 Hz, 19 helix), 8.17 (1H, d, J= 8.4 Hz, H3 helix), 8. 12 (3H, m, H3 trimer, H4 helix and trimer), 8.07 (1H, d, J = 8.4 Hz, H8 helix), 7.95 (1H, d, J = 8. 4 Hz, H8 trimer), 7.73 (3H, m, H'trimer and H6, H' helix), 7.66 (1H, dd, J= 6.8, 1.2 Hz, H6 trimer), 6.94 (2H, s, HPh helix), 6. 87 (2H, s, HPh trimer), 3.93 (1H, s, central CH2 helix), 3.78 (1H, s, central CH2 trimer), 1.99 (6H, s, CH3 helix), 1.79 (6H, s, CH3 trimer).

IR: o = 2908 (w), 1633 (m), 1588 (m), 1557 (m), 1506 (m), 1477 (m), 1463 (m), 1380 (m), 1337 (m), 1303 (m), 1228 (m), 1119 (m), 1143 (m), 989 (w), 936 (w), 823 (vs), 780 (m), 750 (m), 680 (m) cm-'.

Coordination of LMe to copper (I) : LMe (0.02g, 0. 04mmol) was dissolved in chloroform and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] BF4 (0.015g, 0.04 mmol) in methanol was added to give a dark violet solution. The solution was heated under reflux overnight and then cooled to room temperature. A dark violet solid precipitated from the solution and was collected by vacuum filtration, washed with methanol and dried in vacuo under P40, o (0.04g, 80%).

Mass spectrum (FAB) m/z = 1278 [Cu2(LMe) 2 (BF4)], 1191 [Cu2 (LMe) 21, 1126 [Cu (LMe) 2], 672 [Cu2 (LMe) (H20)], 594 [Cu (LMe)].

Positive-ion ESI (MeCN): m/z = 1279 ([Cu2(LMe)2(BF4)]+), 595 ([Cu2(LMe)2]2+).

Elemental analysis calculated (%) for [Cu2 (C37H32N4)2] (BF4) 2: C: 65.1, H: 4.7, N: 8.2 ; found: C: 55.6, H: 4.6, N: 7.2.

'H NMR (300MHz, CD3CN, 298 K): ä = 8. 86 (1H, s, H'), 8.80 (1H, d, J= 8.4 Hz, H9), 7.95 (2H, br, H3, H4), 7.65, (1H, br, H7, H8), 7.44 (2H, br, H6), 6.97 (1H, br, HPh), 6.68 (1H, br, HPh), 3.90 (1H, s, CH2), 1.55 (3H, br, CH3).

1H NMR (500MHz, CDzCIz, 283 K): a = 8.86 (1H, s, H'helix), 8.79 (2H, m, H'trimer and H9 helix), 8.73 (1H, d, J= 8.1 Hz, H9 trimer), 8.21 (2H, d, J= 8.1 Hz, H3 helix and trimer), 8. 10 (2H, dd, J = 8. 1,3. 1 Hz, H4helix and trimer), 7.76 (1H, d, J = 8.7 Hz, H8 trimer), 7.68 (3H, m, H7 trimer and H7,H8 helix), 7.50 (2H, dd, J = 8. 1,6. 8 Hz, H6 helix and trimer), 6.98 (2H, m, HPh helix and trimer), 6.75 (2H, m, HPh helix and trimer), 3.93 (1H, s, central CH2 helix), 3.78 (1H, s, central CH2 trimer), 2.10 (6H, s, CH3 helix), 1.89 (6H, s, CH3 trimer).

IR: o = 2969 (m), 2910 (m), 1606 (s), 1588 (s), 1508 (s), 1476 (m), 1435 (s), 1379 (m), 1334 (w), 1303 (w), 1228 (m), 1196 (m), 1143 (m), 1052 (vs), 937 (w), 874 (w), 831 (w), 784 (w), 752 (m) cm-1.

UV-Vis (MeCN): 365 (21830), 380sh (4400), 638sh (a = 2400) nm.

Preparation of LEt : To a stirred solution of 2-quinolinecarboxaldehyde (0.068g, 0.43 mmol) in ethanol (30 ml) at room temperature was added dropwise an ethanolic solution of 4,4'-methylenbis (2, 6-diethylaniline) (0.0667g, 0.215 mmol). After the addition was complete, the reaction mixture was stirred at room temperature for 24 hours. The resultant precipitate was filtered off, washed with ethanol and dried in vacuo under P4010 to afford 0.063g (50%) of yellow solid.

Mass spectrum (FAB): m/z = 589 [M+H] + Elemental analysis calculated (%) for C41H40N4: C : 83. 6, H: 6. 8, N: 9.5 ; found: C: 83.4, H: 6.8, N: 9.5.

'H NMR (300MHz, CD3CN, 298 K): a = 8. 60 (1H, br, H'), 8. 44 (1H, d, J = 8.6 Hz, H3/4), 8. 32 (2H, br, H3/4, H9), 7.90 (1H, d, J= 8.5 Hz, H6/7), 7. 80 (1H, t, J= 7.9 Hz, H...), 7.64 (1H, t, J = 7. 9 Hz, H6/7), 6. 98 (2H, s, HPh), 3.96 (1H, s, central CH2), 2. 53 (4H, qd, J= 7.5 Hz, CH2), 1.14 (6H, t, J = 7.5 Hz, CH3).

IR: o = 2961 (s), 2927 (m), 2870 (m), 1630 (s), 1594 (m), 1559 (m), 1501 (m), 1453 (s), 1427 (m), 1376 (m), 1306 (w), 1255 (w), 1235 (w), 1198 (s), 1142 (s), 1112 (m), 1079 (w), 1059 (w), 1014 (w), 982 (w), 953 (w), 932 (w), 888 (s), 878 (s), 868 (w), 835 (vs), 788 (m), 770 (m), 740 (vs), 702 (m) cm-'.

Coordination of LEt to silver (I) : Care was taken to exclude light during the following procedure. LEt (0.02g, 0.03 mmol) in chloroform and silver (I) hexafluorophosphate (0.007 g, 0.03 mmol) in methanol were stirred at room temperature for 24 hours. X-ray quality, orange crystals were obtained by slow diffusion of diizopropyl ether into solution (0.042g, 75%).

Mass spectrum (FAB) m/z = 1537 [Ag2(LEt)2 (PF6) ], 1392 [Ag2 (L) 2], 1285 [Ag (LEt) 2] Positive-ion ESI (MeCN): m/z = 1285 ([Ag(LEt)2]+), 696 ([Ag2(LEt)2]2+) Elemental analysis calculated (%) for [Ag2(C41H40N4)2](PF6)2#2H2O: C: 57.3, H: 4.9, N: 6.5 ; found: C: 57.0, H: 5.0, N: 6.3.

'H NMR (300MHz, CD3CN, 298 K): c = 8. 81 (2H, m, H', H3/4), 8.13 (2H, m, H3/4, H5/8), 7.95 (1H, d, J = 8. 3 Hz, H5/8), 7.70 (1H, ddd, J = 8.1, 6.9, 1.1 Hz, H6/7), 7.62 (1H, ddd, J = 8. 4,6. 9,1. 5 Hz, H6/7), 6.81 (2H, br, HPh), 3.83 (1H, s, central CH2), 2.48 (4H, br, CH2), 0.7 (6H, br, CH3).

IR: # = 2964 (m), 2871 (m), 1633 (m), 1614 (w), 1588 (w), 1558 (w), 1505 (m), 1458 (m), 1433 (m), 1380 (m), 1337 (m), 1305 (w), 1226 (w), 1190 (m), 1143 (m), 990 (m), 877 (m), 827 (vs), 787 (m), 775 (m), 753 (s), 693 (w), 666 (w) cm-'.

Coordination of L3 to Fe (II) To a stirred solution of acetylpyrazine (0.041 g, 0.30 mmol) and ground 3 A dried molecular sieves in methanol was added dropwise 4,4'methyledianiline (0.029 g, 0.15 mmol) in methanol and a few drops of glacial acetic acid. The mixture was heated under reflux for 24 h. The molecular sieves were removed by filtration and the filtrate treated with FeCl2 4H20 (0.019 g, 0.10 mmol) and refluxed for 2 hours. The purple solution was treated with methanolic ammoniumhexafluorophosphate solution, the resulting precipitate were filtered off and dried over P401o. Recrystalization from CH3CN/diisopropylether afforded 0.052g, yield 58% of purple crystals of [Fe2L3] (PF6) 'HNMR (300MHz, CD3CN, 298K) d = 9.68 (1H, br, H6/5), 8. 82 (1H, br, H3), 7.37 (2H, br, H6/5, Hph), 6.77 (1H, d, J= 7.0 Hz, Hph), 6.77 (1H, d, J = 7.0 Hz, Hph), 4.65 (1H, d, J = 6.4 Hz, Hph), 4.04 (1H, s, CH2), 2.47 (3H, s, CH3).

Copper (I) metallo-supramolecular compounds may be produced as shown in J. Chem.

Soc, Dalton Trans. , 2002,164-169. See also Chem. Commun., 1999,2033-2024.

Triple helicates and planar dimers from silver (1) coordination to bis-pyridylimine ligands may be produced as shown in J. Chem. Soc. , Dalton Trans, 2002, 1635-1641.

Metallo-supramolecualar cylinders may be produced as shown in Angew. Chem. Int.

Ed. 2001,40, No. 5 and Chem. Commun. 1997 1807.

Synthesis of [Cu2 (L3) 2] [PF6] 2 Ligand L3 (0.296 g, 0.503 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] [PF6] (0.187 g, 0.503 mmol) was added to give a dark red solution. The solution was heated under reflux overnight and then cooled to room temperature. A dark red solid precipitated from the solution on standing and was collected by filtration and dried with diethyl ether (0.682 g, 85 %).

IR (solid): 2961m, 2922m, 2867m, 1606m, 1591m, 1509m, 1459m, 1431m, 1373m, 1326w, 1295m, 1252w, 1225m, 1194m, 1136m, 1054w, 988m, 941m, 874m, 824s, 781s, 746s, 634m cm''.

Mass spectrum (ESI): m/z 1450 {Cu2 (L3) z (PF6)} +, 652 {Cu2 (L') 2} .

(Found: C, 61.0 ; H, 5.0 ; N; 7.0. Calc. for Cu2Cs2HsoNsP2Fl2-H20 : C, 61.1 ; H, 5.1 ; N, 7. 0 %). 1H NMR (CD2Cl2) : os 8. 86 (1H, s, Hi), 8.77 (1H, d, J=8. 3Hz, H3/4), 8.17 (1H, d, J= 8. 5 Hz, H3/4), 8.08 (1H, d, J= 8.1 Hz, Huis), 7.67 (1H, ddd J= 8. 1,6. 2,1. 7 Hz, H6X7), 7.54 (2H, m, H5/s & H6/7), 7.02 (1H, s, HPh), 6.62 (1H, s, HPh), 3.91 (1H, s, central CH2), 2.72 (1H, m, CH2), 2.52 (1H, m, CH2), 2.12 (2H, m, CH2), 0.84 (3H, t, J= 7.4 Hz, CH3), 0.65 (3H, t, J= 7.5 Hz, CH3).

UV/Vis (MeCN): 641 (e = 2 000), 526 (e = 7 000), 316 (e = 20 000) nm.

Ligand L.

L (C22H22N4) : 6-Methylpyridine-2-carboxaldehyde (2.00 g, 16.51 mmol) and 1, 3-bis (aminomethyl) benzene, (1.11 cm3, 8. 25 mmol) were stirred in diethyl ether (25 cm3) over anhydrous magnesium sulphate for 2 hours. The orange solution was then filtered and concentrated under reduced pressure. An orange solid (2.57 g, 92%) crystallised out of solution over 14 hours in air and was collected by vacuum filtration and washed with ice-cold ethanol. dH(250 MHz; CDC13, 298K): d 8. 56 [2H, s, Hi], 7.95 [2H, d, J= 7.6 Hz, H3], 7.70 [2H, t, J = 7.6 Hz, H4], 7.37 [4H, m, HPh2-5], 7. 28 [2H, d, J= 7.6 Hz, H5], 5.25 [4H, s, CH2], 2.98 [6H, s, CH3] ppm. dc (75.6 MHz; CDC13, 298K): d 163.6 (Ci), 158.5 (C2/6/ph3), 154.3 (C2/6/Ph3), 139.4 (C2/6/Ph3), 129.2 (CPh2/Ph4/Ph5), 128.5 (CPh2/Ph4/Ph5), 127.4 (C Ph2/Ph4/Ph5), 124.9 (Cs), 118.9 (C3), 65.3 (CCH2), 24. 7 (CCH3) ppm. Positive-ion EI, m/z 343 ({M+}, 50%), 236 ({M+-C6H4N2}, 60%), 221 ({M+-C7H7N2}, 100%). Positive-ion CI: m/z 343 ({MH+}, 100%). Accurate mass, positive-ion CI: Found m/z 343.1923 ; Calculated for {C22H22N4H+} 343.1923 ;. nma/ccmi' (KBr) 3062m, 3001m, 2954m, 2910w, 2868m, 2809w, 2018w, 1806w, 1651s, 1606w, 1590s, 1574s, 1491w, 1464s, 1441w, 1412m, 1374w, 1352m, 1327m, 1303w, 1268w, 1254w, 1222w, 1166w, 1086m, 1056w, 1043m, 995m, 984m, 905w, 884w, 803s, 793s, 774s, 746w, 736m, 694m, 650m, 621w, 577w, 546w, 494w.

[Cu2 (L) 2l [BF4] 2 L (0.03 g, 0. 088 mmol) and [Cu (MeCN) 4] [BF4] (0.03 g, 0.095 mmol) were stirred in methanol (40 cm3) under dinitrogen for 14 hours. The resulting red solution was concentrated (in vacuo) and diethyl ether (3 cm3) added. The solution was cooled in ice and the resulting red solid collected by vacuum filtration (0.015 g, 34%).

[Cu2 (L) 2] [PF6] 2 was prepared by an analogous route starting from [Cu (MeCN) 4] [PF6]. d (400 MHz; CD3CN, 233K): #8. 63 [4H, s, Hi], 7. 87 [4H, t, J = 7.9 Hz, H4], 7.64 [4H, d, J = 7.9 Hz, H3], 7.32 [4H, d, J = 7.9 Hz, H5], 7.00 [2H, s, HPh2], 6.96 [2H, t, J = 6.9 Hz, HPh5], 6. 87 [4H, d, J = 6.9 Hz, HPh4], 4.52 [4H, d, J = 13.3 Hz, CH2], 4.22 [4H, d, J = 13.3 Hz, CH2], 2.08 [12H, s, CHa] ppm. Positive ion FAB : m/z 899 {Cu2 (L) 2 (BF4)+}, 812 {Cu2 (L) 2+}, 405 {Cu (L)+}. vmax/cm-1 (KBr) 2800-3050w, 1624m, 1590m, 1464m, 1383m, 1257m, 1124m, 1084s, 1029m, 797m, 736w, 712w, 533w, 521w, 486w.

#max/nm (e/mol-1 dm-3 cm-1) (MeCN): 490 (3000). Calculated for [Cu2 (C22H22N4) 2] [BF4] 2. 1H2O : C 52.7, H 4.6, N 11. 2 ; Found: C 52.6, H 4.37, N 10.9%.

[Ag2 (L) 2] [PF6] 2 Care was taken throughout this procedure to exclude light. L (0.03 g, 0. 088 mmol) and silver acetate (0.015 g, 0.088 mmol) were heated to reflux for one hour in methanol (30 cm3). The resulting clear solution was then filtered through celite and treated with methanolic ammonium hexafluorophosphate. The resulting white precipitate was collected by vacuum filtration (0.025 g, 48%). The analogous tetrafluouroborate salt [Ag2 (L) 2] [BF4] 2was prepared in a similar fashion by treating the clear solution with ammonium tetrafluoroborate. ci (250 MHz ; CD3CN, 298K): d 8.57 [4H, s, Hui3, 7.95 [4H, t, J = 7. 8 Hz, H4], 7.60 [4H, d, J = 7.8 Hz, H3], 7.43 [4H, d, J = 7. 8 Hz, Hs], 7.25 [2H, s, Hph2], 7.06 [6H, s, HPh4&Ph5], 4.37 [8H, s, CH2], 2.03 [12H, s, CH3] ppm. Positive ion FAB: mlz 1045 {Ag2(L)2(PF6)+}, 900 {Ag2 (L) 2+}, 791 {Ag(L)2+}, 593 {Ag (L)(PF6)+}, 559 {Ag2(L)+}, 451 {Ag (L)+}. vmax/cm-1 (KBr) 2914w, 1645m, 1593m, 1459m, 1383w, 1328w, 1257m, 1212w, 1165m, 1095m, 1050w, 1004w, 839s, 793m, 732w, 655w, 557s. Calculated for [Ag2 (C22H22N4) 2] [PF6] 2. 1. 33CHCl3 : C 40.3, H 3.4, N 8.3 ; Found: C 40.3, H 3.1, N 8.1%.

[Cu3 (L) 3 (OAc) 3] [PF6] 3 L (0.05 g, 0. 146 mmol) in 1: 1 methanol/ethanol (7.5 cm3) solution was added to a stirred solution of copper acetate monohydrate (0.029 g, 0.146 mmol) also in 1: 1 methanol/ethanol (7. 5cm3) solution, under dinitrogen in an ice-water bath. The green solution was then treated with methanolic ammonium hexafluorophosphate. The resulting green precipitate was collected by vacuum filtration and washed with ice-cold diethyl ether (5 cm3), yield (0.047g, 57%). Positive ion ESI (methanol): m/z 1686. 7 ({Cu3 (L) 3 (OAc) 3 (PF6) 2+}, 5%). 1075.7 ({Cu2 (L) 2 (OAc) 2 (PF6)+}, 22%). 1016.6 ({Cu2 (L) 2 (OAc) 3+}, 15%). 955.5 ({Cu2 (L) 2 (OAc) 2+}, 6%). 812.9 ({Cu3 (L) 3 (OAc) 2 (PF6) 2+}, 13%). 769.9 ({Cu3 (L) 3 (OAc) 3 (PF6) 2+}, 15%). 464.2 ({Cu2 (L) 2 (OAc) 2 21} or {Cu3 (L) 3 (OAc) 3}, 100%). 435 ({Cu2 (L) 2 (OAc) 2+}, 74%).

Positive ion ESI (Acetonitrile): m/z 1686. 4 ({Cu3 (L) 3 (OAc) 3 (PF6) 22+}, 5%). 1075.6 ({Cu2 (L) 2 (OAc) 2 (PF6)+}, 6%). 464.4 ({Cu2 (L) 2 (OAc) 2'1 or {Cu3 (L) 3 (OAc) 32+}, 100%).

435.5 ({Cu2 (L) 2 (OAc) 2+}, 26%). 290.2 ( {Cu2 (L) 2 (OAc) 3+}, 26%). vmax/cm-1 (solid) 2850-3100w, 1652w, 1601m, 1575w, 1538w, 1464m, 1442m, 1418w, 1378m, 1326m, 1257m, 1224m, 1171m, 1013w, 831s, 791m, 739m, 704m, 667m, 621w. Calculated for [Cu3 (L) 3 [OAc] 3 [PF6] 3. 3H20 : C 45.9, H 4.3, N 8.9 ; Found: C 45.7, H 4.0, N 8.6%.

[Ni3 (L) 3 (OAc) 3] [PF6] 3 L (0. 50 g, 1. 59 mmol) and nickel (II) acetate (0.40 g, 1. 59 mmol) were stirred in ethanol (30 cm3) for 1 hour, sonicated for 5 minutes, and treated with ethanolic ammonium hexafluorophosphate. A green precipitate formed immediately.

After 24 hours green crystals formed which were collected for X-Ray analysis by manual separation before the bulk precipitate was collected by vacuum filtration, yield (0.56 g, 63%). [Ni3 (L) 3 [OAc] 3 [BF4] 3 was prepared by an analogous route, adding ammonium tetrafluoroborate in place of ammonium hexafluorophosphate. Positive ion ESI (methanol): m/z 1670.0 ({Ni3 (L) 3 (OAc) 3 (PF6) 2+}, 100%). 1063.5 ({Ni2 (L) 2 (OAc) 2 (PF6)+}, 13%). 805.3 ({Ni3 (L) 3 (OAc) 2 (PF6) 22+}, 17%). 762.4 ({Ni3 (L) 3 (OAc) 3 (PF6) 2+}, 20%). 488.4 ({Ni3 (L) 3 (OAc) 2 (PF6)3+}, 7%). 459.8 ({Ni3 (L) 3 (OAc) 33+} or {Ni2 (L) 2 (OAc) 22+}, 10%). Positive ion ESI (Acetonitrile): mlz 1670.0 ({Ni3 (L) 3 (OAc) 3 (PF6) 2+}, 24%). 1063.5 ({Ni2 (L) 2 (OAc) 2 (PF6)+}, 16%). 805. 3 ({Ni3 (L) 3 (OAc) 2 (PF6) 22+}, 23%). 762.4 ({Ni3 (L) 3 (OAc) 3 (PF6)2+}, 60%). 488.4 ({Ni3 (L) 3 (OAc) 2 ({PF6)3+}, 35%). 459.8 ({Ni3 (L) 3 (OAc) 33+} or {Ni2 (L) 2 (OAc) 22+}), 100%. vmax/cm-1 (solid) 3100-3500w, 1652m, 1601m, 1538m, 1456m, 1418w, 1393w, 1327w, 1256m, 1223w, 1171w, 1107w, 1059w, 1007m, 946w, 830s, 788s, 740m, 702w, 680m, 665m, 625w. Calculated for [Ni3 (L) 3] [OAc] 3 [PF6] 3.3H20 : C 46.3, H 4.4, N 9.0 ; Found: C46. 1, H, 4. 0, N8. 8%.

Ligand L: 2-Pyridine carboxaldehyde (1.4 cm3, 15.1 mmol) and 4, 4'-methylenedianiline (1.5 g, 7.6 mmol) were stirred in ethanol (25 cm3) at room temperature for 12 hours.

The yellow solid that precipitated was collected by vacuum filtration, recrystallised from ethanol and dried in vacuo (2.6 g, 84 %).

IR (KBr): 1624m, 1581m, 1565m, 1502s, 1465s, 1433s, 1347m, 1197w, 1146m, 1088w, 989s, 880m, 865m, 827s, 783s cm-1.

Mass spectrum (=ve FAB): m/z 377 {M + H}.

(Found: C, 79.4 ; H, 5.3 ; N, 14.7. Calc. For C25H20N4#0.125H2O : C, 79.3 ; H, 5.4 ; N, 14.8 %).

'H NMR (CDC13) (250 MHz) at 298 K: d 8. 73 (2H, d, J= 4.0 Hz, H6), 8.65 (2H, s, Hi), 8. 23 (2H, d, J= 7.0 Hz, H3), 7. 83 (2H, td, J= 8.3, 1.9, 0.6 Hz, H4), 7. 39 (2H, ddd, J= 7.6, 4.9, 1.2 Hz, H5), 7.29 (8H, m, Hph), 4.07 (2H, s, CH2).

[Fe2L3] [PF6] 4: Ligand L (0.0301 g, 0.08 mmol) and iron (II) chloride (0.0106 g, 0.05 mmol) were heated under reflux in methanol (20 cm3) under dinitrogen for 2 hours. The resulting purple coloured solution was cooled and treated with saturated methanolic ammonium hexafluorophosphate. On cooling a purple precipitate separated and was isolated by filtration (0.0408 g, 84 %).

IR (KBr): 1615m, 1585m, 1558w, 1502s, 1473m, 1440m, 1414w, 1302s, 1256w, 1239m, 1206s, 1162m, llllm, 1018s, 832vs crr-'.

Mass spectrum (+ve FAB): m/z 808 {FeL2}, 827 {FeL2F}, 883 {Fe2L2F}, 902 {Fe2L2F2}, 919 {Fe2L2F3}, 1047 {Fe2L2 (PF6) F2}, 1386 {Fe2L3 (PF6)}, 1403 {Fe2L3 (PF6) F}, 1421 {Fe2L3 (PF6) F2}, 1531 {Fe2L3 (PF6)2}, 1551 {Fe2L3 (PF6) 2F}, 1675 {Fe2L3 (PF6) 3}.

Mass spectrum (ESI): m/z 311 {Fe2L3}4+ 100 %, 421 {Fe2L3F} 3+ 1 %, 462 {F32L3(PF6)}3+ 1 %.

(Found: C, 47.3 ; H, 3.3 ; N, 8.7. Calc. For Fe2C7sH6oNl2P4F24-4H20 : C, 47.6 ; H, 3.6 ; N, 8. 9%).

'H NMR (CD3CN) (400 MHz) at 233 K: d 8. 75 (1H, s, Hi), 8.48 (1H, d, J = 7. 4 Hz, H3), 8.34 (1H, t, J = 7.4 Hz, H4), 7. 68 (1H, t, J= 6.4 Hz, Hs), 7.22 (2H, m, H6, ph), 6.55 (1H, d, J = 7. 8 Hz, Hph), 5.75 (1H, d, J = 6.9 Hz, HPh), 5.17 (1H, d, J = 7.4 Hz, Hph) 3.98 (1H, s, CH2).

'H NMR (CD3COCD3; 300 MHz; 298K) d 9.32 (1H, s, Hi), 8. 80 (1H, d, J= 7.7 Hz, H3), 8. 56 (1H, t, J = 7.7 Hz, H4), 7.95 (1H, t, J= 6. 2 Hz, Hs), 7.71 (1H. d, J= 5. 1 Hz, H6), 7.05 (2H, br d, Ha/b), 5.75 (2H, br d, Ha/b), 4.06 (1H, s, CH2).

UV/Vis (MeCN): 524 (e = 11,000), 572 (e = 15,000) nm.

The chloride salt was prepared by an analogous route.

1H NMR (D20) (300 MHz) at 298K : d 8.89 (1H, s, Hi), 8.44 (1H, d, J= 7.7 Hz, H3), 8.27 (1H, t, J = 7. 7 Hz, H4), 7.58 (1H, t, J= 6.6 Hz, H5), 7.27 (1H, d, J= 5.5 Hz, H6), 7.1 (1H, br, Hph), 6.6 (1H, br, Hph), 5.7 (1H, br, Hph), 5.3 (1H, br, Hph), 3. 89 (1H, s, CH2).

'H NMR (CD30D) (300 MHz) at 298K d 9.17 (1H, s, Hi), 8.72 (1H, d, J= 7.5 Hz, H3), 8.48 (1H, t, J = 7.5 Hz, H4), 7. 85 (1H, t, J= 6.5 Hz, H5), 7.45 (1H, d, J= 5.3 Hz, H6), 7.1 (2H, br, Hph), 5.6 (2H, br, Hph), 4.05 (1H, s, CH2).

[Ni2L3] [PF6] 4 : Ligand L (0.0309 g, 0.08 mmol) and nickel (II) acetate (0.0136 g, 0.05 mmol) were heated under reflux in methanol (20 cm3) for 12 hours. The resulting yellow coloured solution was cooled and treated with saturated methanolic ammonium hexafluorophosphate. On cooling, yellow crystals separated and were isolated by filtration (0.0360 g, 72 %).

IR (KBr) : 1635w, 1598s, 1504m, 1446w, 1308m, 1206m, 1018s, 841vs cm-2.

Mass spectrum (+ve FAB): m/z 434 {NiL}, 810 {NiL2}. 1014 {Ni2L2(PF6)}, 1032 {Ni2L2 (PF6) F}, 1052 {Ni2L2 (PF6) F2}, 1391 {Ni2L3 (PF6)}, 1410 {Ni2L3 (PF6) F}, 1429 {Ni2L3 (PF6) F2}, 1537 {Ni2L3(PF6)2}, 1554 {Ni2L3 (PF6) 2F}, 1682 {Ni2L3 (PF6) 3}.

Mass spectrum (ESI): mlz 312 {Ni2L3}4+ 100 %, 464 {Ni2L3 (PF6)} 3+ 10 %, 768 {Ni2L3 (PF6) 21 2+ 1 %, 1073 {Ni4L6 (PF6) 5}3+ 1 %, 1681 {Ni2L3 (PF6) 3}+ 1 %.

(Found: C, 47.2 ; H, 3.5 ; N, 8. 6. Calc. For Ni2C7sH6oNl2P4F24-4H20 : C, 47.4 ; H, 3.6 ; N, 8. 9 %).

[Co2L3][PF6]4: Ligand L (0.0307 g, 0. 08 mmol) and cobalt acetate (0.0135 g, 0.05 mmol) were heated under reflux in methanol (20 cm3) for 12 hours. The resulting orange coloured solution was cooled and treated with saturated methanolic ammonium hexafluorophosphate. On cooling, orange crystals separated and were isolated by filtration (0. 0368 g, 74 %).

IR (KBr): 1628s, 1596m, 1505m, 1444m, 1308m, 1205m, 1017s, 814vs cm-1.

IH NMR (CD3CN ; 400 MHz; 298K) d 245,87, 72, 51, 22,15, 0-5, -22 'H NMR (D20 ; 400 MHz; 298K) d 244,87, 72,51, 23,15, 1, -20 Mass spectrum (+ve FAB) : m/z 435 {CoL}, 811 {CoL2}, 889 {Co2L2F}, 908 {Co2L2F2}, 923 {Co2L2F3}, 1015 {Co2L2 (PF6) }, 1034 {Co2L2(PF6)F}, 1053 {Co2L2 (PF6) F2}, 1392 {Co2L3(PF6)}, 1411 {Co2L3 (PF6) F}, 1426 {Co2L3 (PF6F}, 1537 {Co2L3 (PF6) 2}, 1556 {Co2L3 (PF6) 2F}, 1682 {Co2L3(PF6)3}.

Mass spectrum (ESI): m/z 313 {Co2L3} 4+ 100 %, 465 {Co2L3 (PF6)} 3+ 5 %, 769 {Co2L3 (PF6) 2}2+, 20 %, 1073 {Co4L6 (PF6) 5 13+ 5 %, 1225 {Co6L9 (PF6) 8141 1 %, 1683 {Co2L3 (PF6) 3}+ 10 %. <BR> <BR> <P>(Found: C, 47.5; H, 3.3; N, 9.0. Calc. For Co2C75H60N12P4F24#4H2O: C, 47.4; H3, 3.6; N,<BR> <BR> <BR> <BR> <BR> 8. 9%).

Preparation of L: 4,4'-Methylenedianiline (0.793 g, 4 mmol) and 4 (5) -imidazolecarboxaldehyde (0.768 g, 8 mmol) were stirred in methanol (30 ml) for 10 minutes, two drops of glacial acetic acid were then added and the mixture was further refluxed for 2 hours. An off-white solid precipitated and was collected by filtration, washed with methanol and dried in vacuo over P40, o. Yield: 95 %. m. p.

260-261°C. Anal. Calcd. for C21Ho8N6 : C, 71.2 ; H, 5.1 ; N, 23.7%. Found: C, 70.9 ; H, 5.1 ; N, 23.5%. Mass spectrum (EI+) : m/z : 354 [M+]. tH NMR (DMSO, 400 MHz, 300K) : d 12.8 (1H, s, NH), 8.42 (1H, s, Hi.), 7.80 (1H, s, H2/4), 7.62 (1H, s, H2X4), 7.23 (2H, d, J = 7.8 Hz, Hph), 7.15 (2H, d, J = 7.8 Hz, Hph), 3.98 (1H, s, CH2). IR data (KBr, cm-1) : 3060sh, 3024m, 2970w, 2906w, 2832m, 2647w, 2589w, 1629vs, 1600s, 1546vw, 1502s, 1438m, 1414w, 1351w, 1331w, 1298w, 1222m, 1202w, 1170w, 1155sh, 1094m, 1014w, 991m, 918w, 874m, 845m, 808w, 787w, 752w, 710w, 622s, 601w, 539m, 480vw.

Preparation of the Complexes [Fe2 (L) 3] [PF6] 4 (1). Ligand L (0.106 g, 0.3 mmol) and iron (II) chloride tetrahydrate (0.040 g, 0.2 mmol) were stirred in methanol (15 mL) for 45 minutes. The resulting orange solution was filtered through Celite and treated with methanolic ammonium hexafluorophosphate (excess). Slow evaporation of the solvent at room temperature yielded an orange microcrystalline product, which was collected by filtration, washed with cold methanol and dried in vacuo over P4010. Yield: 67 % Anal. Calcd. for [Fe2 (C2lHlsN6) 3] [PF6] 4. 2H20 : C, 42.2 ; H, 3.2 ; N, 14.1%. Found: C, 41.9 ; H, 3.0 ; N, 14.0%. Mass Spectrum (FAB): m/z 1609 [Fe2 (L) 3 (PF6) 3], 1463 [Fe2 (L) 2 (L-H) (PF6) 2], <BR> <BR> <BR> <BR> 1317 [Fe2 (L) (L-H) 2 (PF6) ], 1171 [Fe2 (L-H) 3], 837 [Fea (L-H) 2 (F) ], 818 [Fe2 (L-H) 2], 766 [Fe (L) (L-H) ], 409 [Fe (L-H) ]. Positive-ion ESI (MeCN): m/z 1609 ([Fe2 (L) 3 (PF6) 3] +), 1315 ( [Fe2 (L) (L-H) 2 (PF6)]+), 1256 ( [Fe2 (L) 2 (PF6) 3] +), 1171 ( [Fe2 (L-H) 3]'), 732 ( [Fe2 (L) 3 (PF6) 2] 2+), 658 ( [Fe2 (L) 2 (L-H) (PF6)] 2-1), 585 ( [Fe2 (L) (L-H) 2] 2+), 439 ( [Fe2 (L) 3 (PF6)] 3+), 409 ([F3(L-H)]+), 391 ( [Fe2 (L) 2 (L-H)]"), 355 ( [HL] ).'H NMR (CD3CN, 500 MHz, 298K): d 158. 3 (1H, br s, H2), 92.1 (1H, s, NH), 42. 5 (1H, br s, Him), 37.9 (1H, s, H4), 24.7 (1H, s, CH2), 14.6 (2H, s, Hph),-5. 6 (2H, br s, Hph) UV-Vis (MeCN) : Imax [nm] (e [M-1cm-1]) : 283 (53200), 313 (58000), 443 (1390), 810 (10). IR data (KBr, cm-') : 3622w, 3396br, 3134br, 2934w, 2860w, 2588vw, 1621vs, 1600sh, 1556w, 1501m, 1437m, 1347vw, 1294w, 1232w, 1208w, 1174vw, 1144vw, 1094m, 101 lw, 848vs, 757sh, 710w, 617m, 559s. Orange crystals suitable for X-ray analysis were grown by slow evaporation of a methanolic solution of complex 1.

[Fe2 (L) 3] [BF4] 4 (2). Ligand L (0.127 g; 0.36 mmol) and iron (II) chloride tetrahydrate (0. 048 g, 0.24 mmol) were stirred in methanol (15 mL) for 40 minutes. The resulting orange solution was filtered through Celite and treated with methanolic ammonium tetrafluoroborate (excess) to yield an orange product, which was isolated by filtration, washed with methanol and dried in vacuo over P4O10. The product was then dissoluted in 10 mL of acetonitrile. The solution was filtered through Celite, concentred in vacuo, diluted with 15 ml of methanol and allowed to stay at room temperature for 24 hours.

An orange polycrystalline powder resulted, which was collected by filtration, washed with cold methanol and finally dried in vacuo under P40 ; o. Yield: 65 %. Anal. Calcd. for [Fe2 (C21H18N6)3][BF4]4.2H2O : C, 48.5 ; H, 3.7 ; N, 16.2%. Found: C, 48.4 ; H, 3.4 ; N, 16.0%. Mass Spectrum (FAB): m/z 1347 [Fe2 (L) 2 (L-H) (BF4) 2], 1259 <BR> <BR> <BR> <BR> [Fe2 (L) (L-H) 2 (BF4) ], 1171 [Fe2 (L-H) 3], 837 [Fe2 (L-H) 2 (F) ], 818 [Fe2 (L-H) 2], 766 [Fe (L) (L-H)], 409 [Fe (L-H) ]. Positive-ion ESI (MeCN) : m/z 586 ( [Fe2 (L) (L-H) 2]2+), 420 ( [Fe2 (L) 3 (BF4)] 3+), 409 ([Fe(L-H)]+), 355 ([HL] +).'H NMR (CD3CN, 500 MHz, 298K) : d 159. 2 (1H, br s, H2), 92.7 (1H, s, NH), 42.9 (1H, br s, Him), 38.1(1H, s, H4), 24.8 (1H, s, CH2), 14. 7 (2H, s, HPh), -5. 7 (2H, br s, Hph). UV-Vis (MeCN): Lax [nm] (e [M-'cm-']) : 285 (54400), 310 (58300), 438 (1400), 822 (12). IR data (KBr, cm-') : 3376w, 3131br, 2932w, 2856w, 2588vw, 1620vs, 1599s, 1555w, 1501m, 1437m, 1347vw, 1294m, 1232w, 1207w, 1082vs, 1054sh, 935vw, 892w, 861w, 814w, 757w, 710w, 617m, 547w, 534w, 522w. X-ray quality, orange crystals of 2 were obtained from a saturated acetonitrile solution by diffusion of di (isopropyl) ether.

[Fe2 (L) 3] [C104] 4 (3): Ligand L (0.096 g; 0.27 mmol) and iron (II) chloride tetrahydrate (0.036 g, 0.18 mmol) were stirred in methanol (15 mL) for 45 minutes. The resulting orange solution was filtered through Celite and treated with 0.4 mmol of lithium perchlorate dissoluted in 10 ml of MeOH/H20 (4: 1) solvent mixture. An orange product instantaneously formed, and was collected by filtration, washed with methanol and dried in vacuo over Polo. Yield: 72%. Anal. Calcd. for [Fe2 (C21H18N6)3][ClO4]4.2H2O : C, 47.0 ; H, 3.6 ; N, 15.7%. Found: C, 46.9 ; H, 3.3 ; N, 15.5%. Mass Spectrum (FAB): m/z 1473 [Fe2 (L) 3 (CI04) 3], 1372 [Fe2 (L) 2 (L-H) (CI04) 2], 1271 [Fe2 (L) (L-H) 2 (CIO4)], 1171 [Fe2 (L-H) 3], 817 [Fe2 (L-H) (L-2H) ], 766 [Fe (L) (L-H)], 409 [Fe (L-H) ]. Positive-ion ESI (MeCN): m/z 1470 ([Fe2(L)3(ClO4)3]+), 685 ([Fe2(L)3(ClO4)2]2+), 636 ([Fe2 (L) 2 (L-H) (ClO4)] 2+), 586 ([Fe2 (L) (L-H) 2]2+), 424 ( [Fe2 (L) 2 (C104)] 3+), 409 ([Fe (L-H)] +), 355 ([HL]+). 1H NMR (CD3CN, 500 MHz, 298K) : d 158. 3 (1H, br s, H2), 92.1 (1H, s, NH@, 42. 5 (1H, br s, Him) 37. 9 (1H, s, NH@, 24.7 (1H, s, CH2), 14.6 (2H, s, Hph),-5. 6 (2H, br s, Hph). W-Vis (MeCN): lmax [nm] (e [M-'cmi']) : 286 (57400), 306 (sh), 438 (1410), 834 (12). IR data (KBr, cm-') : 3242sh, 3135br, 2933w, 2856w, 2588vw, 1620vs, 1599s, 1556w, 1501s, 1436m, 1346vw, 1294m, 1232w, 1207w, 1088vs, 1008m, 969vw, 934vw, 892m, 861w, 814m, 757w, 710w, 625s, 617s, 547w. Orange crystals suitable for X-ray analysis were obtained by slow diffusion, in an H-shaped tube of two 10-4 M methanolic solutions containing [Fe2 (L) 3]Cl4 and LiClO4, respectively.

CAUTION! No problems were encountered during the preparation of the perchlorate derivative described above. However, suitable care must be taken when handling such potentially explosive materials.

[Ni2 (L) 3] [PF6] 4 (4). Ligand L (0.053 g; 0.15 mmol) and nickel (II) chloride hexahydrate (0.024 g, 0.10 mmol) were stirred in methanol (10 mL) for 30 minutes. The resulting green solution was treated with methanolic ammonium hexafluorophosphate (excess), filtered through Celite and the filtrate allowed to standing for 48 hours at 4 °C. Green crystals formed and were collected by filtration, washed several times with small amounts of cold methanol, and finally dried in vacuo over P4O10. Yield : 68 %. Anal.

Calcd. for [Ni2 (C21H] 8N6) 3] [PF6J4. 2H20 : C, 42. 1 ; H, 3.2 ; N, 14.0%. Found: C, 41.9 ; H, 3.1 ; N, 13.8%. Mass Spectrum (FAB): m/z 1615 [Ni2 (L) 3 (PF6) 3], 1469 [Ni2 (L) 2 (L-H) (PF6) 2], 1323 [Ni2 (L) (L-H) 2 (PF6)], 1177 [Ni2 (L-H) 3], 823 [Ni2 (L-H) (L-2H)], 412 [Ni (L-H) ]. Positive-ion ESI (MeCN) : m/z 1615 ( [Ni2 (L) 3 (PF6)3]+), 733 ( [Ni2 (L) 3 (PF6) 2] 2+), 660 ( [Ni2 (L) 2 (L-H) (PF6)]2+), 588 <BR> <BR> <BR> ( [Ni2 (L) (L-H) 2]2+), 441 ( [Ni2 (L) 3 (PF6)] 3+), 411 ( [Ni (L-H) ] +), 392 ( [Ni2 (L) 2 (L-H) ] 3+), 355 ([HL]+). 1H NMR (CD3CN, 500 MHz, 298K) : d 229.0 (1H, br s, H2), 93.1 (1H, s, NH), 58. 7 (1H, br s, Him) 40.9 (1H, s, H4), 27.5 (1H, s, CH2), 15.4 (2H, s, Hph),-6. 7 (2H, br s, Hph). UV-Vis (MeCN): 1max [nm] (e [M-lcm-']) : 262 (48300), 308 (66200), 554 (24), 900 (25). IR data (KBr, cm-') : 3629w, 3379m, 3139w, 3099w, 3033w, 2933w, 2847w, 2589vw, 1622vs, 1600s, 1560w, 1499s, 1438m, 1337vw, 1289m, 1234w, 1207w, 1174vw, 1151w, 1094m, 1017m, 964vw, 847vs, 755sh, 710w, 618m, 604sh, 558s, 425vw. Single crystals suitable for X-ray analysis were directly collected from the reaction mixture, after standing at 4 °C for 2 days.

[Co2 (L) 3] [PF6] 4 (5). Ligand L (0.053 g; 0.15 mmol) and cobalt (II) chloride hexahydrate (0.024 g, 0.10 mmol) were stirred in methanol (15 mL) for 30 minutes. 2 mL of water were added and the reaction mixture was further stirred for 45 minutes.

The resulting orange solution was treated with potassium hexafluorophosphate (excess), filtered through Celite and the filtrate allowed to stay for 24 hours at room temperature.

Orange crystals formed and were collected by filtration, washed with methanol, and finally dried i71 vacuo over P4O10. Yield: 75%. Anal. Calcd. for [Co2 (C21H18N6)3] [PF6] 4 . CH30H. H20 : C, 42. 4; H, 3.3 ; N, 13.9%. Found: C, 42.4 ; H, 3.0 ; N, 13.8%. Mass Spectrum (FAB) : mlz 1615 [Co2 (L) 3 (PF6) 3], 1469 [Co2 (L) 2 (L-H) (PF6) 2], 1323 [Co2 (L) (L-H) 2 (PF6)], 1177 [Co2 (L-H) 3], 823 [Co2 (L-H) (L-2H) ], 412 [Co (L-H)].

Positive-ion ESI (MeCN): m/z 1615 ([Co2 (L) 3 (PF6) 3]+), 1174 ([Co2 (L-H) 3] +), 734 ([Co2(L)3(PF6)2]2+), 662 ([Co2 (L) 2 (L-H) (PF6)] 2+), 588 ([Co2 (L) (L-H) 2]2+), 442 ([Co2 (L) 3 (PF6)] 3+), 411 ([Co(L-H)]+), 392 ([Co2 (L) 2 (L-H)] 3+), 355 ( [HL] +).'H NMR (CD3CN, 500 MHz, 298K): d 235.0 (1H, br s, H2), 99.6 (1H, s, NH), 52.9 (1H, s, H4), 23.8 (1H, br s, Him), 22.1 (1H, s, CH2), 2.0 (2H, s, HPh), -19.1 (2H, br s, Hph). UV-Vis (MeCN) : ilmax [nm] (s [M-1cm-1]) : 285 (55600), 318 (38250), 490 (42). IR data (KBr, cm-1) : 3629w, 3379m, 3127w, 3096w, 3031w, 2929w, 2847w, 2589vw, 1621vs, 1600s, 1559w, 1500s, 1439m, 1336vw, 1290m, 1233w, 1207w, 1174vw, 1150w, 1094m, 1014m, 965vw, 847vs, 756sh, 710w, 618m, 602sh, 558s, 419vw. X-Ray quality, orange crystals were obtained from a saturated 1: 1 acetonitrile : acetone solution by slow diffusion of diethylether.

[Mn2 (L) 3] [PF6] 4 (6): Ligand L (0.106 g; 0.3 mmol) and manganese (II) chloride tetrahydrate (0.039 g, 0.2 mmol) were stirred in methanol (15 mL) for 45 minutes. The resulting yellow solution was treated with methanolic ammonium hexafluorophosphate (excess), filtered through Celite and allowed to stay at room temperature overnight. A pale yellow polycrystalline product formed and was isolated by filtration, washed with methanol, and dried in vacuo over P4Owo. Yield : 74 %. Anal. Calcd. for [Mn2(C21H18N6)3][PF6]4 .H2O : C, 42.7 ; H, 3.2 ; N, 14.2%. Found: C, 42.5 ; H, 3.0 ; N, 14.2%. Mass Spectrum (FAB): mlz 1607 [Mn2 (L) 3 (PF6) 3], 1461 [Mn2 (L) 2 (L-H) (PF6) 2], 1315 [Mn2 (L) (L-H) 2 (PF6) ], 1169 [Mn2 (L-H) 3], 815 [Mn2 (L-H) (L-2H)], 408 [Mn (L-H)]. Positive-ion ESI (MeCN): m/z 731 ( [Mn2 (L) 3 (PF6) 2] 2+), 658 ( [Mn2 (L) 2 (L-H) (PF6)] 2+), 585 ( [Mn2 (L) (L-H) 2] 2+), 408 ([Mn (L-H) ] +, [Mn2 (L-H) 2] 2+), 355 ( [HL] +). UV-Vis (MeCN) #max [nm] (e [M-'cm-']) : 267 (51600), 318 (112100). IR data (KBr, cm-') : 3631w, 3386m, 3142w, 3102w, 3037w, 2927w, 2848w, 2590vw, 1623vs, 1600s, 1556w, 1502s, 1440m, 1347vw, 1295m, 1232w, 1207w, 1178vw, 1152w, 1093m, 1005m, 970vw, 847vs, 756sh, 710w, 620m, 602sh, 558s, 425vw. Yellow crystals suitable for X-ray analysis were grown by slow diffusion of diethylether into a solution of complex in 1: 1 acetonitrile/acetone.

LMe (R= Me) and LEt (R= Et) Synthesis of Ligands L"and L" Ground 3A dried molecular sieves (5 g) and 4,4'-methylenebis (2, 6-diethylaniline) or 4,4'-methylenebis (2, 6-dimethylaniline) (0.678 g, 2.67 mmol) were added to methanol (90 cm3) and stirred under a nitrogen atmosphere until the methylenedianaline had dissolved (approximately 5 minutes).

Pyridine-2-carboxyaldehyde (0.571 g, 5.34 mmol) was added and the mixture stirred at room temperature for 24 hours. The molecular sieves were removed by filtration and the filtrate concentrated by rotary evaporation to produce a yellow solid.

LMe Yellow solid (0.934 g, 81 %).

IR (KBr): 2996w, 2905m, 2846w, 1638s, 1583m, 1476s, 1433s, 1385s, 1318w, 1283w, 1200s, 1141m, 1089w, 1042w, 987m, 876m, 837m, 774s, 742m, 695w, 647w, 616w cm-1.

Mass spectrum (+ve CI) : m/z 433 [M+H] +.

(Found: C, 80. 5; H, 6.6 ; N; 13.0. Calc. for C29H28N4 : C, 80. 5; H, 6.5 ; N, 13. 0 %).

1H NMR (CDCl3) : os 8.72 (1H, d, J = 4.9 Hz, H6), 8. 35 (1H, s, Hi), 8. 28 (1H, d, J= 7.9 Hz, H3), 7. 84 (1H, td, J= 7.9, 1.7 Hz, H4X5), 7.40 (1H, ddd, J= 7.5, 4.7, 1.1 Hz, H4/5), 6.94 (2H, s, Hph), 3.85 (1H, s, central CH2), 2.15 (6H, s, CH3).

13C NMR (CDC13) : d 163. 83 C7, 154. 94 C2/8/11, 149. 99 C6, 148. 76 C2/8/11, 137.53 C2/8/11, 137. 11 C4/5, 129. 11 C10 & C12, 127.43 C9 & C13, 125. 68 C4/5, 121. 59 C3, 41.28 C16, 18. 79 C14 & C15.

LEt From 4,4'-methylenebis (2, 6-diethylaniline) (4. 087 g, 13.16 mmol) and pyridine-2-carboxyaldehyde (2.820 g, 26.33 mmol). Yellow solid (5.459 g, 85 %).

IR (KBr): 2953s, 2925s, 2862s, 1642s, 1587s, 1563s, 1468s, 1456s, 1433s, 1381w, 1362w, 1338w, 1314w, 1291m, 1220w, 1192s, 1141s, 1078w, 995s, 936m, 892m, 853s, 770s, 742m, 691w, 659m cm'.

(Found: C, 80.0 ; H, 7.4 ; N; 11.4 Calc. for C33H36N4#0.5CH3OH ; C, 79.7 ; H, 7.6 ; N, 11. 1 %).

Mass spectrum (+ve EI) : m/z 488 [M]+.

'H NMR (CDC13) : d 8.72 (1H, dq, J = 4.9, 0.9 Hz, H6), 8.35 (1H, s, Hi), 8.27 (1H, dt, J = 7. 7, 1. 1 Hz, H3), 7. 85 (1H, td, J = 7.5, 1.1 Hz, H4/s), 7.41 (1 H, ddd, J = 7. 5,4. 9,1. 1 Hz, H4/5), 6.97 (2H, s, Hph), 3.94 (1H, s, central CH2), 2.50 (4H, q, J = 7.5 Hz, CH2), 1.13 (6H, t, J=7. 5Hz, CH3).

13C NMR (CDC13) : d 163. 46 C7, 154. 92 C2/8/11, 150. 00 C6, 147. 96 C2/8/11, 137.57 C2/8/11, 137. 15 C4/5, 133.30 C9 & C13, 127. 34 Cio& C12, 125. 67 C4/5, 121. 59 C3, 41. 54 C18, 25. 11 C14 7 C16, 15. 18 C15 & C17.

Synthesis of [Cun (LMe)n][PF6]n Ligand LMe (0.084 g, 0.19 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] [PF6] (0. 072 g, 0.19 mmol) was added to give a dark red solution. The solution was heated under reflux overnight and then cooled to room temperature. A black solid precipitated from the solution on standing.

This was collected by filtration and washed with diethyl ether (0.173 g, 71 %). X-ray quality crystals were obtained by the slow diffusion of diethyl ether into a solution of the complex in nitromethane.

The same compound can be prepared in a single pot simply by mixing the aldehyde and diamine and then adding the cuprous salt. It can also be prepared in a solventless reaction by grinding the three compounds together.

IR (KBr): 2902w, 1586m, 1474m, 1440m, 1380m, 1303w, 1200m, 1140w, 900w, 836s, 772m, 742w, 558m cm''.

Mass spectrum (ESI): m/z 1135 {Cu2(LMe)2(PF6)}+, 927 {Cu(LMe)2}+, 816 {Cu3 (LMe)3(PF6)}2+, 495 {Cu2 (LMe) 2} 2+, {Cu (LMe)} +.

Mass apectrum (+ve FAB) : m/z 1137 [Cu2 (LMe) 2 (PF6)] +, 495 [Cu2 (LMe) 2] +.

'H NMR : (CD2Cl2) : d 8.67 (4H, d, J= 4. 9 Hz, H6), 8. 49 (3H, s, Hi helix), 8. 40 (1H, s, Hi, trimer), 8. 21 (3H, td, J= 7.7, 1.5 Hz, H4helix), 8.15 (1H, td, J= 7.7, 1.5 Hz, H4 trimer), 7.99 (4H, d, J= 7.9 Hz, H3), 7.85 (3H, ddd, J = 7.7, 5. 1, 1.3 Hz, Hs helix), 7.77 (1H, ddd, J= 7.7, 5.1, 1.3 Hz, Hs trimer), 6.99 (3H, s, HPh helix), 6.90 (2H, s, Hph trimer), 6.67 (3H, s, HPh helix), 3.92 (3H, s, central CH2 helix), 3.76 (1H, s, central CH2trimer), 2.04 (24H, broad s, CH3).

UV/Vis (MeCN): 470 (e = 12 000), 334 (e=28000), 328 (e=75000) nm.

Synthesis of [Cu2 (LEt) 2] [PF6] 2 Ligand LEt (0.107 g, 0.284 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] [PF6] (0.106 g, 0.284 mmol) was added to give a dark red solution. The solution was heated under reflux overnight and then cooled to room temperature. A dark red solid precipitated from the solution on standing and was collected by filtration and dried with diethyl ether (0.336 g, 85 %).

The solid was recrystallised from acetonitrile by the slow diffusion of benzene to afford dark red crystals.

IR (KBr) : 2965m, 2927w, 2867w, 1611m, 1586m, 1556w, 1504w, 1470m, 1436m, 1380m, 1303m, 1252w, 1192m, 1145m, 836s, 772m, 738w, 549s cm'.

Mass spectrum (ESI): m/z 1247 { (LEt) 2 (PF6)} +, 1040 {Cu2 (LEt)(PF6)}+, 551 {cru2 (LEt) 2} 121.

Mass spectrum (+ve FAB) : m/z 1247 [Cu2 (LEt) 2 (PF6)] +.

(Found: C, 56.0 ; H, 5.2 ; N; 7.9. Calc. for Cu2C66H72NsP2FI2-H20 : C, 56. 1; H, 5.3 ; N, 7. 9 %).

'H NMR (CD2CI2) : os 8. 56 (1H, s, Hi), 8. 53 (1H, broad d, J= 4.9 Hz, H6), 8. 22, (1H, td, J = 7.9, 1.4 Hz, H4), 8. 00 (1H, broad d, J = 7.4 Hz, H3), 7. 83 (1H, ddd, J= 7. 8, 4.9, 1.4 Hz, Hs), 7.03 (2H, broad d, J = 1.4 Hz, Hph), 6.52 (2H, broad d, J = 1.5 Hz, Hph), 3. 86 (1H, s, central CH2), 2.68 (2H, m, CH2), 2. 58 (2H, m, CH2), 2.19 (2H, m, CH2), 2.00 (2H, m, CH2), 1.02 (3H, t, J= 7.9, CH3), 0.45 (3H, t, J= 7.4, CH3).

UV/Vis (MeCN): 475 (e = 1300), 339 (e = 42000), 275 (e = 17 000) nm.

Synthesis of [Agn (LMe) n] [PF6] n Care was taken to exclude light during the following procedure. LMe (0.1 g, 0.231 mmol) was dissolved in chloroform and silver (I) hexafluorophosphate (0.058 g, 0.231 mmol) dissolved in methanol was added and stirred at room temperature for 2 hours. The yellow precipitate was collected by vacuum filtration, washed with chloroform and dried in vacuo under P401o (0.22 g, 70%). IR (KBr): 2923m, 2855w, 1643m, 1586m, 1478m, 1439m, 1386m, 1303w, 1260w, 1197w, 1143w, 1007w, 842s, 770m, 741w cm'.

Mass spectrum (ESI): m/z 1225 {Ag2 (LMe) 2 (PF6)} +, 973 {AgF, 883 {Ag3(LMe)3(PF6)}2+, 540 {Ag3(LMe)3}3+, {Ag2(LMe)2}2+.

(Found: C, 49. 4 ; H, 4.1 ; N ; 7.8. Calc. for Ag2C58Hs6NsP2Fl2 2HzO : C, 49.6 ; H, 4. 3 ; N, 8. 0 %).

'H NMR (O-D2CI2, 283 K): os = 8. 75 (2H, s, H ;), 8.41 (1H, d, J= 7.5 Hz, H6helix), 8. 31 (1H, d, J= 6.5 Hz, H6 trimer), 8. 20 (1H, td, J= 7.8, 1.5 Hz, H4helix), 8.15 (1H, td, J= 7.8, 1.5 Hz, H4 trimer), 7.88 (2H, dd, J= 9.7, 7.8 Hz, H3), 7.81 (1H, ddd, J = 7.8, 5.0, 2.8 Hz, Helix), 7.81 (1H, ddd, J = 7.8, 5.0, 2. 8 Hz, Hs trimer), 6.92 (2H, s, Hph helix), 6.85 (2H, s, Hph trimer), 3.92 (1H, s, central CH2 helix), 3.76 (1H, s, central CH2 trimer), 1.94 (6H, s, CH3 helix), 1.77 (6H, s, CH3 trimer).

Synthesis of [Ag2 (LEt)2][PF6]2 Ligand LEt (0.106 g, 0.217 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere and excluding light, silver (I) acetate (0.036 g, 0.217 mmol) was added to give a yellow solution. The solution was heated under reflux in the dark for 1 hour and then cooled to room temperature. The solution was filtered through celite and the yellow filtrate collected. A yellow solid precipitated on addition of excess methanolic [NH4] [PF6] to the filtrate and was collected by filtration (0. 238 g, 74 %). X-ray quality crystals were obtained by the slow diffusion of diethyl ether into a solution of the complex in acetonitrile.

IR (KBr) : 2964m, 2928m, 2870w, 1643s, 1571w, 1473m, 1432w, 1384s, 1309w, 1258w, 1196w, 1145w, 1104m, 903m, 838s, 775w, 611w cm-1.

Mass spectrum (ESI): m/z 1338 {Ag2(LEt)2(PF6)}+, 1083 {Ag (LEt) 2} +, 551 {Ag2 (LEt) 2} 2+ Mass spectrum (+ve FAB) : m/z 1338 [Ag2(LEt)2(PF6)]+.

(Found: C, 52. 8 ; H, 4.9 ; N; 7.3. Calc. for Ag2CsoH4oNsP2FI2-H2O : C, 52.9 ; H, 5.0 ; N, 7. 5%) 'H NMR (CD2C12) : os 8.73 (1H, d, J = 4.9 Hz, H6), 8.47 (1H, d, J = 8.3 Hz, Hi), 8. 22 (1H, td, J= 7.7, 1.7 Hz, H4), 7. 89 (1H, d, J= 7.7 Hz, H3), 7. 83 (1H, dd J= 7.5, 4.7, Hz, H5), 6.71 (2H, s, Hph), 3.79 (1H, s, central CH2), 2.31 (4H, m, CH2), 0.72 (6H, t, J = 7. 4 Hz, CH3).

7.1. 13 Synthesis of Ligand Ls Ground 3 A dried molecular sieves (5 g) and 3,3'-methylenedianiline (0.200 g, 1.009 mmol) were added to toluene (30 cm3) and stirred under a nitrogen atmosphere until the 3, 3'-methylenedianiline had dissolved (approximately 5 minutes).

2-quinolinecarboxaldehyde (0.317 g, 2. 017 mmol) was added and the mixture stirred at room temperature for 24 hours. The molecular sieves were removed by filtration and the filtrate concentrated by rotary evaporation to produce a yellow oil (0.416 g, 87 %).

IR (oil): 2369m, 2356m, 1626m, 1585s, 1558w, 1505s, 1482m, 1424m, 1357w, 1308w, 1240w, 1200w, 1146w, 1115w, 1084w, 954w, 904w, 828s, 752s, 730s, 690s cm~'.

Mass spectrum (+ve FAB) : m/z 477 [M+H] +.

1H NMR (CDCl3) : os 8.72 (2H, s, H@), 8. 29 (2H, d, J = 8.7 Hz, H3), 8. 19 (2H, d, J = 8. 7 Hz, H4), 8.09 (2H, d, J= 8. 5 Hz, H9), 7.80 (2H, dd, J=8. 1,1. 3 Hz, H6), 7.70 (2H, ddd, J= 9.2, 5.1, 1.7 Hz, Hs), 7.54 (2H, ddd, J = 8. 1,7. 0,1. 1 Hz, H7), 7.32 (2H, t, J = 7.6 Hz, Hc), 7.10 (6H, m, Has Hb & Hd), 4.03 (2H, s, central CH2).

13C NMR (CDCl3) : # 161.28 Ci, 155.24 C2, 151. 45 C5/10/12/16, 148.35 C5/10/12/16, 142.48 C5/10/12/16, 137.06 C4, 130.33 Cs, 130.10 C9, 129. 86 Clan 129.44 C5/10/12/16, 128. 63 C7, 128. 11 C6, 128.08 Cl7 122.53 Ci5, 119. 370, 3, 119.08 C3, 42.27 CH2.

Synthesis of [Cu2(L5)2][PE6]2 Ligand Ls (0.173 g, 0.363 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] [PF6] (0.135 g, 0.363 mmol) was added to give a purple solution. The solution was heated under reflux overnight and then cooled to room temperature. A purple solid precipitated from the solution on standing and was collected by filtration and dried with diethyl ether (0.373 g, 75 %). The solid was recrystallised from acetonitrile by the slow diffusion of benzene to afford dark purple crystals.

IR (solid): 1594m, 1298w, 1143w, 1002w, 837vs, 779m, 745m, 677m cm-1.

Mass spectrum (ESI): m/z 1225 {Cu2 (Ls) 2(PF6)}+, 1016 {Cu(L5)2}+, 539 {Cu2 (L5) 2} 2+, {Cu (L5)} +.

SUBSTITUTE SHEET (RULE 26) (Found: C, 53.7 ; H, 3.4 ; N; 7.5. Calc. for Cu2C66H48N8P6F12#(H2O)6: C, 53.6 ; H, 4.0 ; N, 7.6 %).

'H NMR (CD2Cl2) : os 9.35 (7H, s, Hi helix), 9.25 (2H, s, Hi box), 8.73 (2H, d, J= 8. 5 Hz, H3/4 box), 8. 72 (7H, d, J = 8.3 Hz, H3/4 helix), 8. 32 (7H, d, J = 8.3 Hz, H3/4 helix), 8.26 (2H, d, J = 8. 5, H3/4 box), 8.02 (9H, d, J = 7.9 Hz, H6/9), 7.77 (9H, d, J = 7.9 Hz, H6, 9), 7. 57 (27H, m, Hb/d,H7 & H8), 7.31 (9H, t, J= 7.3 Hz, He), 6.82 (9H, d, J= 7.3 Hz, b/d), 6.67 (9H, s, Ha), 3.51 (7H, s, central CH2helix), 3.46 (2H, d, J= 5. 3 Hz, central CH2 box).

W/Vis : # 569.0 nm, # 131 000 dm3mol-1cm-1; # 340.2 nm, # 97 000 dm3mol-1cm-1 ; 1 254.4 nm, e 16 300 dm3mol-1cm-1.

The tetrafluoroborate salt was prepared in 75 % yield by the same route replacing [Cu (MeCN) 4] [BF4] with [Cu (MeCN) 4] [PF6].

The perchlorate salt was prepared in 72 % yield by the same route followed by the addition of excess methanolic Na04Cl.

Synthesis of [Ag2(L5)2][PF6]2 Ligand Ll (0.186 g, 0.390 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere and excluding light, silver (I) acetate (0.065 g, 0.390 mmol) was added to give a yellow solution. The solution was heated under reflux in the dark for 40 minutes and then cooled to room temperature. The solution was filtered through celite and the yellow filtrate collected. A yellow solid precipitated on addition of excess methanolic [NH4] [PF6] to the filtrate and was collected by filtration (0.410 g, 72%).

IR (solid): 2992w, 2620w, 1590m, 1500m, 1370w, 1339w, 1142w, 989w, 842vs, 792w, 743w cm-1.

Mass spectrum (ESI): m/z 1314 {Ag2 (L5) 2(PF6)}+, 1060 {Ag(L5)2}+, 839 {Ag2(L5)(PF6)}+, 584 {Ag2(L5)2}2+, {Ag(L5)}+.

'H NMR : (CD2Cl2) : 9.23 (2H, s, Hi), 8.77 (2H, d, J= 8. 0 Hz, H3/4), 8. 33 (2H, d, J= 8. 0 Hz, H3/4) 8. 09 (2H, d, J=8. 0Hz, H6/9), 7.92 (2H, d, J = 7.4 Hz, Hb/d), 7.62 (6H, m, H6/9, H7 & H8), 7.19 (2H, t, J= 7.4 Hz, Hc), 6.96 (2H, s, Ha), 6.85 (2H, d, J= 7.4 Hz, Hb/d), 3. 58 (2H, s, central CH2).

The tetrafluoroborate salt was prepared in 70 % yield by the same route followed by the addition of excess methanolic [NH4] [BF4].

The perchlorate salt was prepared in 74 % yield by the same route replacing silver (I) perchlorate instead of silver (I) acetate.

Synthesis of Ligand L'" 2-nitrosopyridine (0.003 g, 0.024 mmol) was dissolved in dichloromethane.

4, 4'-methylenedianiline (0.002 g, 0.012 mmol) and glacial acetic acid (1 drop) were added and the orange solution was stirred at room temperature overnight. The solution was evaporated to dryness to provide an orange coloured solid (0 003 g, 73 %).

IR (KBr): 3064w, 2928w, 1643m, 1585s, 1497m, 1463m, 1410s, 1308w, 1260w, 121 Iw, 1148s, 1104m, 988m, 876m, 818w, 794s, 740s, 658w, 615w cm-1.

Mass spectrum (+ve FAB) : m/z 379 [M+H] +.

(Found: C, 70.4 ; H, 4.7 ; N; 21.5. Calc. for C23H18N6#0. 5H20: C, 70.7 ; H, 5.1 ; N, 21. 5 %).

1H NMR (CDCl3) : d 8. 75 (1H, dq, J= 4.7, 0.75 Hz, H6), 8. 03 (2H, d, J= 8. 5 Hz Hax 7.92 (1H, td, J= 7.9, 1.9 Hz, H4/5), 7. 83 (1H, dt, J= 7.9, 1.0 Hz, H3), 7.40 (3H, m, HA & H4/5), 4.17 (1H, s, central CH2).

13C NMR (CDC13) : d 163. 5 vC2/7/10, 152. 0 C2/7/10, 149. 9 C6, 145. 3 C2/7/io, 138. 7 C4/5, 130. 2 C8/9/11/12, 125. 5 C4/5, 124. 4 C8/9/11/12, 115. 9 C3, 42. 2 C13.

Synthesis of [Cu2(L10)2][PF6]2 Ligand Ll° (0.020 g, 0.053 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] [PF6] (0.020 g, 0.053 mmol) was added to give a dark red solution. The solution was heated under reflux overnight and then cooled to room temperature. A dark red solid precipitated from the solution on standing and was collected by filtration and dried with diethyl ether (0.053 g, 85 %). The solid was recrystallised from nitromethane by the slow diffusion of diethyl ether to afford dark red crystals.

IR (KBr): 2914w, 2846w, 1628m, 1594s, 1492w, 1468w, 1444m, 1420m, 1381s, 1308w, 1274w, 1231w, 1192w, 1153s, 1012w, 954w, 843s, 789s, 741m cell. Mass spectrum (ESI): m/z 1029 {Cu2(L10)2(PF6)}+, 650 {Cu2 (Ll°) (PF6)} +, 253 {Cu2(L10)}2+.

NMR (CD2Cl2) : os 8.51 (1H, d, J = 7.7 Hz, H3), 8.47 (1 H, d, J = 4.7 Hz, H6), 8. 38 (1H, t, J= 7.5, 1.7 Hz, H4/5), 7.89 (2H, d, J = 8. 3 Hz, HPh), 7.83 (1H, ddd J= 7.3, 5.1, 1.1 Hz, H4/5), 7.30 (2H, broad s, Hph), 4.02 (1H, s, central CH2).

UV/Vis (MeCN): 573 (e= 16 000), 390 (e= 87 000), 339 (e= 188 000), 227 (e= 170 000) nm.

Synthesis of [Ag2(L10)2][PF6]2 Ligand L" (0.011 g, 0.029 mmol) was dissolved in methanol and whilst stirring and excluding light, silver (I) acetate (0.005 g, 0.029 mmol) was added to give a yellow solution. The solution was heated under reflux in the dark for 30 minutes and then cooled to room temperature. The solution was filtered through celite and the yellow filtrate collected. A dark yellow solid precipitated on addition of excess methanolic [NH4] [PF6] to the filtrate and was collected by filtration (0.029 g, 78 %).

IR (KBr): 2918w, 2846w, 1599s, 1502m, 1458w, 1415s, 1386m, 1279s, 1250s, 1221s, 1153s, 1104w, 1027m, 1007m, 845s, 789s, 736m, 639s cm-1.

Mass spectrum (ESI): m/z 1338 {Ag2 (L") 2 (PF6)} +, 1083 {Ag (L10) 2} +, 551 {Ag2(L10)2}2+.

'H NMR (CD2Cl2) : #8. 64 (1H, d, J= 4.5 Hz, H6), 8. 34, (2H, m, H3 &H4i5), 7.93 (2H, d, J= 8.3 Hz, Hph), 7.79 (1H, ddd, J= 7.3, 4.9, 2. 8 Hz, H4/5), 7. 36 (2H, d, J= 8.5 Hz, Hph), 4.10 (1H, s, central CH2).

Synthesis of [Fe2(L10)3][PF6]4 Ligand L10 (0.019 g, 0.050 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere, FeCl2. 4H20 (0.007 g, 0.034 mmol) was added to give a dark green solution. The solution was heated under reflux for three days and then cooled to room temperature. Excess methanolic [NH4] [PF6] was added and a dark green solid precipitated from the solution on standing. This was collected by filtration and dried with diethyl ether (0.049 g, 79 %).

IR (KBr): 2923w, 2851w, 1633m, 1599s, 1497w, 1449m, 1415m, 1361s, 1313m, 1264w, 1240m, 1201w, 1167m, 1104w, 1051w, 1012w, 959w, 846s, 779s, 741m cm-'.

Mass spectrum (ESI): m/z 768 {Fe2 (L'") 3 (PF6) 2} 2+, 464 {Fe2(L10)3(PF6)}3+, 312 {Fe2(L10)3}4+.

'H NMR (CD3CN): oS 9.13 (1H, d, J= 4.5 Hz, H6), 8. 69, (1H, t, J= 7.3 Hz, H4/5), 7.88 (1H, t, J = 6.0 Hz, H4/5), 7.02 (3H, m, 3 & HPh), 6.25 (2H, d, J = 7.7 Hz, Hph), 4.10 (1H, s, central CH2).

W/Vis (MeCN): 597 (s= 31 000), 395 (e= 119 000), 295 (e= 126 000), 235 (e= 181 000), 206 (e= 304 000) nm.

Synthesis of Half-Ligand L11 2-nitrosopyridine (0.03 g, 0.278 mmol) was dissolved in dichloromethane. An excess of 4, 4'-methylenedianiline (0.220 g, 1.112 mmol) and glacial acetic acid (1 drop) were added and the orange solution was stirred at room temperature overnight. The solution was evaporated to dryness to provide an orange coloured solid. Column chromatography was carried out on silica gel using CH2Cl2 as an eluant. The product was collected at Rf= 0.4 (0.03 g, 40 %).

IR (solid): 3434s, 3342s, 3015m, 2916m, 1618s, 1600s, 1581s, 1519s, 1464m, 1412s, 1309m, 1280s, 1225m, 1173m, 1136s, 1100m, 1045w, 1008w, 986w, 861w, 824m, 795s, 776s, 740s, 655w, 618w cm~'.

Mass spectrum (+ve FAB) : m/z 289 [M+H] +.

'H NMR (CDC13) : # 8.70 (1H, d, J= 3.4 Hz, H6), 7.99, (2H, d, J= 8.5 Hz, Hph), 7.92 (1H, td, J= 7.5 Hz, H4/5), 7.83 (1H, d, J= 7.7 Hz, H3), 7.41 (1H, dd, J = 7.4, 4.5 Hz, H4/5), 7.36 (2H, d, J= 8.3 Hz, Hph), 7.03 (2H, d, J= 8.3 Hz, Hph), 6.67 (2H, d, J= 8.3 Hz, Hph), 3. 98 (2H, s, CH2), 3.64 (2H, broad s, NH2).

Synthesis of Asymmetric Ligand L" The half-ligand L"was dissolved in methanol. One equivalent of pyridine-2-carboxaldehyde was added and the orange solution was stirred at room temperature for seven days. The orange solution was then reduced to dryness to produce an orange coloured oil. The'H NMR spectrum contained overlapping resonances, some of which corresponded to the starting material pyridine-2-carboxaldehyde.

Mass spectrum (+ve FAB) : m/z 378 [M+Hy +.

Synthesis of [Cu2(L12)2][PF6]2 Ligand L12 was dissolved in methanol and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] [PF6] was added to give a dark red solution. The solution was heated under reflux overnight and then cooled to room temperature. A dark red solid precipitated from the solution on standing and was collected by filtration and dried with diethyl ether. The solid was recrystallised from acetonitrile by the slow diffusion of diethyl ether to afford dark red crystals. 'H NMR spectroscopy in both CD3CN and CDzCI2 provided overlapping signals and in both solvents there was evidence for the existence of more than one species in solution. X-ray quality crystals were obtained by the slow diffusion of diethyl ether into a solution of the complex in acetonitrile.

IR (solid): 2950w, 1630w, 1591s, 1501m, 1470m, 1439m, 1420w, 1392w, 1365m, 1299w, 1272w, 1225w, 1190w, 1155m, 1093w, 1003m, 972w, 816s, 774s, 727m, 649w, 637w cmi'.

Mass spectrum (ESI): m/z 1027 {Cu2 (L12) 2 (PF6)} +, 817 {Cu (L12)}+, 441 {Cu (L12)} +.

UV/Vis (MeCN): 570 (#= 11 000), 337 (#= 85 000), 236 (#= 67 000) nm.

Synthesis of Ligand L" 2-nitrosopyridine (0.106 g, 0. 981 mmol) was dissolved in dichloromethane.

4, 4-diaminodiphenylether (0.098 g, 0.491 mmol) and glacial acetic acid (1 drop) were added and the orange solution was stirred at room temperature overnight. The solution was evaporated to dryness to provide an orange coloured solid (0. 138 g, 74 %).

IR (solid): 1579s, 1482s, 1462s, 1373m, 1291w, 1237s, 1132s, 1089m, 988m, 957w, 828m, 781m, 731m, 610w cm''.

Mass spectrum (+ve EI): m/z 382 [M+2H]+.

'H NMR (CDC13) : b8. 72 (1H, d, J=4. 9Hz, H6), 8.07, (2H, d, J=9. 0Hz, Hph), 7. 88 (1H, td, J= 8. 1,1. 9 Hz, H4/5), 7.79 (1H, d, J= 8.1 Hz, H3), 7. 38 (1H, dd, J= 7.4, 4.9, 1.3 Hz, H4/5), 7.18 (2H, d, J= 8.9 Hz, Hph).

13C NMr (CDCl3) : b163. 2 C2/7/10, 160.1 C2/7/10, 149.9 C6, 148. 0 C2/7/10, 138. 9 C4/5, 126.1 C8&12/9&11, 125. 6 c4/5, 119. 9 C8&12/9&11, 116. 0 Cs.

Synthesis of [Cu2(L15)2][BF4]2 Ligand Ll5 (0.042 g, 0.111 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] [BF4] (0. 035 g, 0.111 mmol) was added to give a dark solution. The solution was heated under reflux overnight and then cooled to room temperature. A black solid precipitated from the solution on standing and was collected by filtration and dried with diethyl ether (0.076 g, 65 %).'H NMR spectroscopy revealed a broad set of peaks indicating the presence of a copper (II) species.

IR (solid): 1574s, 1482s, 1379m, 1309w, 1247s, 1136s, 1048s, 872m, 835m, 780m, 736w, 637w cni-1.

Mass spectrum (ESI): m/z 973 {Cu2 (Lt5) 2 (BF4)} +, 823 {Cu(L15)2}+, 443 {Cu (Lt5) 3+.

'H NMR (CD3CN) : #8. 44 (1H, broad s, H6), 8.13, (2H, broad m, H3 & H4/5), 7.95 (2H, broad d, J = 8.5 Hz, Hph), 7.62 (1H, broad m, H4/5), 7.00 (2H, broad d, J = 8. 5 Hz, Hph).

UV/Vis (MeCN) : 573 (e= 5 000), 347 (s= 80 000) nm.

Synthesis of [Ag2(L15)2][PF6]2 Ligand L" (0.013 g, 0.035 mmol) was dissolved in methanol and whilst stirring and excluding light, silver (I) acetate (0.006 g, 0.035 mmol) was added to give a yellow solution. The solution was heated under reflux in the dark for 30 minutes and then cooled to room temperature. The solution was filtered through celite and the yellow filtrate collected. A dark yellow solid precipitated on addition of excess methanolic [NH4] [PF6] to the filtrate and was collected by filtration (0.031 g, 70 %).

IR (solid): 2934w, 1571s, 1486s, 1431m, 1408m, 1307w, 1225s, 1128s, 1097w, 1003m, 813s, 770m, 727w, 634w cm-'.

Mass spectrum (+ve FAB) : m/z 1121 [Ag2 (L15)2(PF6)]+, 869 [Ag (L15) 2] +.

(Found: C, 42.2 ; H, 2.6 ; N; 13.0. Calc. for Ag2C44H32N, 202P2F, 2 : C, 41.7 ; H, 2.6 ; N, 13. 3 %).

'H NMR (CD3CN) : ces8. 71 (1H, d, J = 3.2 Hz, H6), 8.10, (3H, m, HPh& H4/5), 7.86 (1H, d, J= 7. 9 Hz, H3), 7.56 (1H, dd, J= 7. 4,5. 8 Hz, H4/5), 7.30 (2H, dd, J = 9.0 Hz, HPh).

Synthesis of Ligand L16 2-nitrosopyridine (0.042 g, 0.389 mmol) was dissolved in dichloromethane.

3, 3-methylenedianiline (0.039 g, 0.194 mmol) and glacial acetic acid (1 drop) were added and the orange solution was stirred at room temperature overnight. The solution was evaporated to dryness to provide an orange coloured solid (0.056 g, 76 %).

Mass spectrum (+ve CI) : m/z 379 [M+H] +.

'H NMR (CDC13) : #8. 73 (1H, d, J= 4.7 Hz, H6), 7.93, (3H, m Hb, Hd & H4/5), 7.81 (1H, d, J = 8. 1 Hz, H3), 7.47 (1H, t, J = 7.7 Hz, He), 7.40 (2H, m, H4/5 & Ha), 4.19 (1H, s, central CH2).

Synthesis of [Cu2(L16)2][BF4]2 Ligand Ll6 (0. 105 g, 0.278 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] [BF4] (0. 087 g, 0.278 mmol) was added to give a dark red solution. The solution was heated under reflux overnight and then cooled to room temperature. A dark red solid precipitated from the solution on standing and was collected by filtration and dried with diethyl ether (0.217 g, 74 %).

IR (solid): 1595m, 1571m, 1494w, 1455w, 1439m, 1385m, 1272w, 1229m, 1143m, 1046s, 941s, 785s, 735m, 696m, 665m cm-'.

Mass spectrum (ESI): m/z 969 {Cuz (L16) 2 (BF4)}', 819 ICu (L") 2}', 441 feu2 (L16)2}2+; {Cu(L16)}+.

'H NMR (CD3CN) : d 8. 54 (1H, d, J = 7.2 Hz, H3), 8. 45, (2H, m H6& H4/5), 7.95 (1H, d, J= 8.3 Hz, Hb/d), 7.83 (1H, t, J= 6.4 Hz, H4/s), 7. 39 (1H, t, J= 7.7 Hz Hc), 7.15 (1H, d, J= 7.4 Hz Hb/d), 6.95 (1H, s, Ha), 3.66 (1H, s, central CH2).

UV/Vis (MeCN): 575 (e=11000), 336 (e=77000) nm.

Synthesis of [Ag2(L16)2][PF6]2 Ligand L16 (0.048 g, 0.127 mmol) was dissolved in methanol and whilst stirring and excluding light, silver (I) acetate (0.021 g, 0.127 mmol) was added to give a yellow solution. The solution was heated under reflux in the dark for 30 minutes and then cooled to room temperature. The solution was filtered through celite and the yellow filtrate collected. A dark yellow solid precipitated on addition of excess methanolic [NH4] [PF6] to the filtrate and was collected by filtration (0.107 g, 76 %). X-ray quality crystals were obtained by the slow diffusion of diethyl ether into a solution of the complex in deuterated acetonitrile.

IR (solid): 1600m, 1497w, 1475w, 1441m, 1305w, 1221m, 1140m, 1100w, 1070w, 912m, 875m, 820s, 806s, 780s, 743m, 684m, 633w cm~'.

Mass spectrum (+ ve FAB) : m/z 1117 [Ag2 (L16)2(PF6)]+.

(Found: C, 43.2 ; H, 2.8 ; N; 13.0. Calc. for Ag2C46H36N,2P2F, 2-H20 : C, 43.2 ; H, 3.0 ; N, 13.1 %).

'H NMR (CD3CN) : os 8.59 (1H, d, J= 4.0 Hz, H6), 8.27, (2H, td, J= 7. 7,1. 7 Hz H4/s), 8.14 (1H, d, J= 7.9 Hz, H3), 7.70 (2H, m, H4 s & Hb/d), 7.43 (1H, s, Ha), 7. 35 (1H, t, J = 7.7 Hz, Hc), 7.26 (1H, d, J= 7.4 Hz, Hb/d), 3.85 (1H, s, central CH2).

Synthesis of Ligand LI8 2-nitroso-6-methylpyridine (0.034 g, 0.279 mmol) was dissolved in dichloromethane. 1,4-phenylenediamine (0.015 g, 0.139 mmol) and glacial acetic acid (1 drop) were added and the orange solution was stirred at room temperature overnight. The solution was evaporated to dryness to provide an orange coloured solid (0.032 g, 74 %).

IR (solid): 1649m, 1599s, 1564s, 1509m, 1455w, 1432m, 1303s, 1373s, 1326s, 1299s, 1229m, 1198m, 1124s, 980m, 898w, 851m, 834m, 778s, 727m, 602w cm-1.

Mass spectrum (+ve CI) : m/z 317 [M+H] +.

'H NMR (CDC13): 6 8. 18 (2H, s, Hph), 7.90 (1H, d, J=7. 6Hz, H3/5), 7.78 (1H, t, J= 7. 8 Hz, H4), 7.62 (1H, d, J = 8. 0 Hz, H3/5), 2.70 (3H, s, CH3).

13C NMR (CDC13) : os 159. 3 C2/6/9, 154. 3 C2/6/9, 151. 8 C2/6/9, 138. 9 C4, 126. 6 C3/s, 124.9 Cs&io, 11 1. 5C3/5.

Synthesis of Ag (L"),,] [PF6],, Ligand L" (0.015 g, 0.047 mmol) was dissolved in methanol and whilst stirring and excluding light, silver (I) acetate (0.008 g, 0.047 mmol) was added to give a yellow solution. The solution was heated under reflux in the dark for 30 minutes and then cooled to room temperature. The solution was filtered through celite and the yellow filtrate collected. A dark yellow solid precipitated on addition of excess methanolic [NH4] [PF6] to the filtrate and was collected by filtration (0. 016 g, 61 %).

IR (solid): 1592m, 1567w, 1467m, 1434w, 1379w, 1323w, 1298w, 1261m, 1217m, 1173m, 1140m, 1088m, 101 lm, 912m, 824s, 728m, 625m cm-1.

Mass spectrum (+ve FAB): m/z 2133 [Ag4 (L18) 4 (PF6) 3]+, 1564 [Ag3 (Lt8) 3 (PF6) 2]+, 995 [Ag2 (LI8) 2(PF6)2]+.

(Found: C, 35.2 ; H, 2. 6; N; 13.6. Calc. for Agn (C18H16N6)n(PF6)n(CHCl3)n/2 : C, 70.7 ; H, 5.1 ; N, 21. 5 %).

'H NMR (CD3CN): # 8. 07 (1H, t, J= 7. 8 Hz, H4), 7.97 (2H, s, Hph), 7.85 (1H, d, J= 7.8 Hz, H3/5), 7.59 (1H, d, J = 7.5 Hz, H3/5), 2.72 (3H, s, CH3).

Synthesis of Ligand L4 3,3'-methylenedianaline (0. 128 g, 0.646 mmol) was dissolved in methanol and whilst stirring, pyridine-2-carboxyaldehyde (0.123 cm3, 1.291 mmol) was added causing the colourless solution to turn pale yellow. The solution was stirred overnight and the solvent removed by rotary evaporation to leave a yellow oil (0.197 g, 81 %).

IR (oil): 3050m, 2365s, 2329s, 2297m, 1742m, 1715w, 1657m, 1585s, 1469s, 1437m, 1343w, 1222w, 1088w, 1048w, 989w, 904w, 864w, 779s, 739,694m, 658m cm-1.

Mass spectrum (+ve FAB) : m/z 377 [M+H]+.

Mass spectrum (+ve El) : m/z 376 [M] +.

'H NMR (CDC13) : os 8.69 (2H, d, J = 4.0 Hz, H6), 8.57 (2H, s, Hi), 8.18 (2H, d, J= 7.9, H3), 7.80 (2H, td, J= 7.4, 1.5 Hz, H4), 7.35 (4H, m, H5 & Hc), 7.15 (6H, m, Ha, Hb& Hd), 3.97 (2H, s, CH2).

'3C NMR (CDCl3) : b 161.02 Ci, 154.94 C2, 151.59 C2/8/12, 150.07 C6, 142.43 C2zsI2, 137.05 C4, 129.80 C10, 127.80 C", 125.70 Cs, 122.41 Cis, 122.27 C3, 119.13 C9, 42.21 CH2.

Synthesis of [Cu2 (L4)2] [PF6] 2 Ligand L4 (0.107 g, 0.284 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] [PF6] (0.106 g, 0.284 mmol) was added to give a dark red solution. The solution was heated under reflux overnight and then cooled to room temperature. A dark red solid precipitated from the solution on standing and was collected by filtration and dried with diethyl ether (0.282 g, 85 %). The solid was recrystallised from acetonitrile by the slow diffusion of benzene to afford dark red crystals.

IR (KBr): 2920w, 1650w, 1591m, 1472m, 1447m, 1303m, 1084w, 844s, 785m, 743m, 698m, 558s cm~'.

Mass spectrum (ESI): m/z 1025 {Cu2 (L4)2(PF6)}+, 816 {Cu(L4)2}+, 504 {Cu2 (L4)} 2+, 440 {Cu2 (L4)2}+.

(Found: C, 51.6 ; H, 3.4 ; N ; 9.5. Calc. for Cu2C50H40N8P2F12 : C, 51.3 ; H, 3.5 ; N, 9. 6 %).

'H NMR (CD3CN) : os 8. 98 (2H, s, Hi), 8.43 (2H, broad d, H6), 8.18 (2H, broad d, H3), 8. 12 (2H, broad t, H4), 7.68 (2H, broad t, Hs), 7.45 (2H, d, J=7. 4Hz, Hb/d), 7. 28 (2H, broad t, He), 6.94 (2H, d, J = 7.4 Hz, Hb/d), 6.64 (2H, s, Ha), 3.65 (2H, s, CH2).

W/Vis : 1507. 2 (8 4000), 330.0 (s 31 300), 241. 8, (# 31 000) nm.

The tetrafluoroborate salt was prepared in 83 % yield by the same route replacing [Cu (MeCN) 4] [BF4] with [Cu (MeCN) 4] [PF6].

The perchlorate salt was prepared in 79 % yield by a similar route followed by the addition of excess methanolic Na04Cl.

Synthesis of [Ag2 (L4) 2] [PF6] 2 Ligand L4 (0.106 g, 0.282 mmol) was dissolved in methanol and whilst stirring under a nitrogen atmosphere and excluding light, silver (I) acetate (0.047 g, 0.282 mmol) was added to give a yellow solution. The solution was heated under reflux in the dark for 1 hour and then cooled to room temperature. The solution was filtered through celite and the yellow filtrate collected.

A yellow solid precipitated on addition of excess methanolic [NH4] [PF6] to the filtrate and was collected by filtration (0.259 g, 73 %).

IR (solid): 2377m, 1680w, 1586m, 1484w, 1437w, 837vs, 775m cm-'.

Mass spectrum (ESI): m/z 1113 {Ag2 (L4)2(PF6)}+, 860 {Ag(L4)2}+, 484 {Ag2(L4)2}2+;{Ag(L4)}+.

(Found: C, 46.9 ; H, 3.1 ; N; 8. 6. Calc. for Ag2C5oH4oNsP2Fi2. 2H20 : C, 46.4 ; H, 3.4 ; N, 8.7 %).

'H NMR (CD3CN) : oS 8.74 (2H, s, Hi), 8. 61 (2H, dd, J= 4.9, 0.6 Hz, H6), 8. 17 (2H, td, 7= 7.9, 1.7 Hz, H4), 7. 98 (2H, d, J= 7.5 Hz, H3), 7.68 (2H, ddd, J = 6.4, 4.9, 1.3 Hz, Hs), 7.32 (2H, d, J = 7.3 Hz, Hbid), 7.21 (2H, t, J= 7.3 Hz, Hc), 6.91 (2H, d, J= 7.3 Hz, Hb/d), 6.75 (2H, s, Ha), 3.60 (2H, s, CH2).

The tetrafluoroborate salt was prepared in 73 % yield by the same route followed by the addition of excess methanolic [NH4] [BF4].

The perchlorate salt was prepared in 70 % yield by the same route replacing silver (I) perchlorate instead of silver (I) acetate.

FURTHER LIGANDS General Preparation of the Ligands. To a solution of toluene (50 cm3) containing vacuum dried 3 A molecular sieves (5 g) and either 4,4'-methylenedianiline or 4, 4'-diaminodiphenyl ether (0.010 mol), two equivalents of the relevant pyridine aldehyde/ketone (0.020 mol) were added. The solution was refluxed for 24 hours.

Following filtration through celite, the solvent was removed in vacuo to yield a yellow solid/oil. The ligand was recrystallised from hot ethanol on several occasions to improve purity. The structures of the ligands investigated are summarised in figure 2.

Preparation of the iron (II) triple helicates. To a refluxing methanolic solution (50 cm3) of each ligand, 2/3 molar equivalents of iron (II) chloride tetrahydrate in the minimum amount of methanol was added. After 2 hours, the deep purple solution, characteristic of iron (II) tris-pyridylimine compounds was observed and the iron (II) triple helicate was precipitated upon the addition of excess ammonium hexafluorophosphate dissolved in methanol. Following filtration, the solid was washed with ether and allowed to dry in a vacuum desiccator. The chloride salt was obtained by anion metathesis in acetonitrile using tetrabutylammonium chloride. The same complexes could be prepared directly by treating mixtures of the diamine and aldehyde/ketone in methanol solution in the appropriate ratios. Complex 1. Anal. Calc. for [Fe2 (C27H24N4) 3] [Cl4]. (FeCl2) 2 : C, 56.6 ; H, 4.2 ; N, 9. 8%. Found: C, 56.6 ; H, 4.3 ; N, 9.7 %. Positive-ion ESI (MeOH): ( [Fe2 (L) 3]4+), 331. 0 ;'H NMR ( (MeOD) 400 MHz, 300 K): #4. 10 (3H, s, Me), 4.64 (3H, s, Me), 4.79 (2H, dd, HPh J = 8.3 Hz, J = 1.5 Hz), 5.57 (2H, dd, HphJ = 8. 3 Hz, J = 1.5 Hz), 6.89 (2H, dd, HphJ = 6.3 Hz), 7.26 (2H, d, H6 J = 6.3 Hz), 7.42 (2H, dd, HphJ= 6.3 Hz, J = 1.1 Hz), 7. 81 (2H, t, Hs J = 6.3 Hz), 8.50 (2H, t, H4 J = 7. 8 Hz), 8. 78 (2H, d, H3 J = 7.8 Hz); Selected IR data (cm-) : 3386w, 1626w, 1588w, 1559w, 1503s, 1474m, 1441m, 1380m, 1334m, 1308w, 1256m, 1166w, 1110w, 1060w, 1019w, 828vs, 771vs, 750vs, 691m, 674m.

Complex 2. Anal. Calc. for [Fe2 (C27H24N4) 3] [PF6] 4 : C, 51. 1; H, 3. 8 ; N, 8.8%. Found: C, 50.8 ; H, 4.1 ; N, 8.8%. Positive-ion ESI (MeCN): m/z ([Fe2 (L2) 3 (PF6) 3] +), 1760.1 ( [Fe2 (L') 3 (PF6) 2]2+), 807.2, ([Fe2 (L2) 3 (PF6)] 3+), 489.9 ([Fe2 (L2) 3] 4+), 331. 2.'H NMR ((CD3CN) 300 MHz, 300 K): #2. 85 (3H, s, Me), 4.02 (1H, s, Me), 5. 28 (1H, bs, Hph), 5.74 (1H, bs, Hph), 6.63 (1H, bs, HPh), 7.06 (1H d, H5 J = 4.5 Hz), 7.31 (1H, bs, Hph), 7.61 (1H, bt, H4 J = 6.0 Hz), 8.15 (1H, d, H3 J = 7.0 Hz), 8.96 (1H, s, Him) ; Selected IR data (cm-') : 3386w, 1626w, 1588w, 1558w, 1503s, 1474m, 1441m, 1380m, 1335m, 1308w, 1256w, 1166w, 1110w, 1060w, 1019w, 828vs, 771vs, 750vs, 691m, 674m.

Complex 3. Anal. Calc. for [Fe2 (C27H24N4) 3] [PF6] 4: C, 51. 1; H, 3.8 ; N, 8.8%. Found: C, 50.8 ; H, 4.0 ; N, 8.6%. Positive-ion ESI (MeCN): m/z ([Fe2(L3)3(PF6)3]+), 1761.1 ([Fe2 (L3) 3 (PF6) 2] 2+), 807.4 ([Fe2(L3)3(PF6)]3+), 490.2 ([Fe2(L3)3]4+), 331.4.'H NMR ( (MeOD) 400 MHz, 300 K): #2. 48 (3H, s, Me), 4.08 (1H, s, Me), 5.59 (2H, vbs, HPh), 7.04 (2H, vbs, Hph), 7.31 (1H, s, Hs), 8. 33 (1H, d, H3/4, J = 7.5 Hz), 8.62 (1H, d, H3/4, J = 8.0 Hz), 9.16 (1H, s, Him) ; Selected IR data (cm-') : 3137w, 2350w, 1625m, 1597w, 1561w, , 1499s, 1354w, 1221m, 1197s, 1106w, 1040m, 1016w, 912s, 836s, 770m, 748w, 658w.

Complex 4. Anal. Calc. for [Fe2 (C29H28N4) 3] [PF6] 4 : C, 52.5 ; H, 4.3 ; N, 8.5%. Found: C, 52.0 ; H, 4.2 ; N, 8. 3%. Positive-ion ESI (MeOH): ( [Fe2 (L 4) 314+), 352.4.'H NMR ( (CD3CN) 300 MHz, 300 K): #2. 35 (3H, s, Me), 2.71 (3H, s, Me), 4.67 (1H, dd, Hph, J = 6. 4 Hz, J = 1. 9 Hz), 5.47 (1H, dd, Hph, J = 6. 0 Hz, J = 2. 0 Hz), 6.76 (1H, dd, HPh, J = 8. 1 Hz, J = 1.8 Hz), 6.93 (1H, d, H5/6, J = 5.6 Hz), 7.31 (1H, dd, Hph, J = 7.6 Hz, J = 1. 8 Hz), 7.51 (1H, d Huis, J = 5.3 Hz), 8.45 (1H, s H3) ; Selected IR data (cm~') : 3386w, 1613w, 1590w, 1503s, 1475m, 1441m, 1379m, 1335m, 1310w, 1221w, 1166w, 1110w, 1042w, 1018w, 828vs, 773vs, 750vs, 691m, 674m.

Complex 5. Anal. Calc. for [Fe2(C24H18N4O)3][Cl]4(H2O)12 : C, 54.1 ; H, 4.5 ; N, 10.5%. Found: C, 54.5 ; H, 4. 1 ; N, 10.0%. Positive-ion ESI (MeOH): ( [Fe2 (L) 3]4+), 311.0 ; 'H NMR ( (D20) 400 MHz, 300 K) : #5. 32 (2H, broad d, HPh J = 6.3 Hz), 5. 86 (2H, broad d, HPh J = 6.0 Hz), 6.38 (2H, bd, Hph J = 5.1 Hz), 6. 98 (2H, bd, Hph J = 6.0 Hz), 7. 25 (2H, d, H6 J= 3. 9 Hz), 7.57 (2H, t, HsJ = 6.0 Hz), 8.23 (2H, t, H4 J = 6.9 Hz), 8. 43 (2H, d, H3 J = 6.6 Hz), 9.01 (2H, s, Him) ; Selected IR data (cm') : 1626w, 1591w, 1488vs, 1441w, 1357w, 1310w, 1227s, 1195s, 1158m, 1105w, 1043w, 1011w, 834vs, 774vs, 691w, 674w.

Complex 6. Anal. Calc. for [Fe2 (C26H22N4O)3] [PF6] 4. 11/2FeCl2 : C, 44.6 H, 3.2 ; N, 8. 0%.

Found: C, 44.4 ; H, 3.4 ; N, 7.7%. Positive-ion ESI (MeCN) : m/z ([Fe2 (L6) 3 (PF6) 3] +), 1765.5 ( [Fe2 (L6) 3 (PF6) 2]2+), 810.2 ( [Fe2 (L6) 3 (PF6)] 3+), 491.9 ([Fe2(L6)3]4+), 332. 8.'H NMR ( (CD3CN) 300 MHz, 300 K): #2. 31 (3H, s, Me), 2.44 (3H, s, Me) 4.88 (1H, d, HPh J = 8.9 Hz), 5.62 (1H, d, HPh J = 7.5 Hz), 6. 57 7 (1H, d, HPh J = 7.1 Hz), 7.10 (1H, d, H6 J = 5.1 Hz), 7.24 (1H, d, HPh J = 8.1 Hz), 7.69 (1H, t, Hs J = 6.0 Hz), 8. 38 8 (1H, t, H4 J = 7.4 Hz), 8.62 (1H, d, H3 J = 7.7 Hz); Selected IR data (cm-1) : 3381w, 1626w, 1588w, 1558w, 1503s, 1474m, 1441m, 1380m, 1335m, 1308w, 1256m, 1166w, 1110w, 1060w, 1019w, 827vs, 771vs, 750vs, 691m, 674m.

Complex 7. Anal. Calc. for [Fe2 (C26H22N40) 3] [Cl] 42FeCl2. 3H20 : C, 52.6 ; H, 4.1 ; N, 9.4%. Found: C, 52.9 ; H, 4.7 ; N, 8. 5%. Positive-ion ESI (MeOH): m/z ( [Fe2 (L') 3 (PF6) 3] +), 1765.3 ([Fe2(L7)3(PF6)2]2+), 810.2 ([Fe2(L7)3(PF6)]3+), 491.9 ([Fe2(L7)3]4+), 332. 6. 'H NMR ( (CD3CN) 400 MHz, 300 K): #2. 87 (3H, s, Me), 5.49 (1H, s, HPh), 5.94 (1H, s, HPh), 6.44 (1H, s, Hph), 7.04 (1H, d, Hs J = 6.1 Hz), 7.22 (1H, s, Hph), 7.60 (1H, t, H4J = 7.2 Hz), 8.15 (1H, d, H3 J = 7.0 Hz), 9.04 (1H, s, Him). Selected IR data (cm-1) : 3356w, 1614w, 1590w, 1490vs, 1446w, 1378w, 1311w, 1231s, 1164m, 1108w, 1038w, 1010w, 833vs, 792s, 691w, 674m.

Complex 8. Anal. Calc. for [Fe2 (C26H22N4O) 3] [PF6] 4#3½EtOH : C, 49.0 ; H, 3.5 ; N, 8.8%.

Found: C, 49.5 ; H, 4. 1 ; N, 8. 3%. Positive-ion ESI (MeCN): m/z ([Fe2(L8) 3 (PF6) 3] +), 1768.5 ([Fe2(L8)3(PF6)2]2+), 810.6 ([Fe2(L8)3(PF6)]3+), 492.2 ([Fe2 (L8) 3] 4+), 332. 9.'H NMR ( (CD3CN) 400 MHz, 300 K): b2. 70 (3H, s, Me), 5.70 (2H, vbs, Hph), 6.70 (2H, vbs, Hph), 7.44 (1H, s, H4), 7.72 (1H, d, H6 J = 5. 9 Hz), 8. 51 (1H, d, H3 J = 7.8 Hz) 9. 30 (1H, s, Him). Selected IR data (cm-1) : 3386w, 1589w, 1562w, 1503s, 1474m, 1441m, 1380m, 1335m, 1308w, 1256m, 1166w, 1110w, 1060w, 1019w, 828vs, 771vs, 750vs, 691m, 674m.

Complex 9. Anal. Calc. for [Fe2 (C26H22N40) 3] [PF6] 4. FeCl2: C, 44.2 ; H, 3.1 ; N, 7.9%.

Found: C, 44.3 ; H, 3.7 ; N, 8.8%. Positive-ion ESI (MeCN): ([Fe2(L9)3]4+), 333. 1. 1H NMR ( (MeOD) 400 MHz, 300 K): #2. 48 (3H, s, Me), 5.77 (2H, vbs, Hph), 6. 78 (2H, vbs, Hph), 7.60 (1H, s, H5), 8. 30 (1H, d, H3/4 J = 8. 0 Hz), 8.73 (1H, d, H3/4 J = 8.0 Hz) 9.60 (1H, s, Him) ; Selected IR data (cm-') : 3386w, 1626w, 1589w, 1558w, 1503s, 1474m, 1441m, 1380m, 1335m, 1308w, 1256w, 1198w, 1166w, 1110w, 1060w, 1019w, 827vs, 771vs, 750s, 691m, 674m.

Complex 10. Anal. Calc. for [Fe2 (C2sH26N40) 3] [PF6] 4. 5½H2O : C, 48. 2; H, 4.3 ; N, 8. 0%. Found: C, 48.0 ; H, 3.9 ; N, 8.0%. Positive-ion ESI (MeOH): Fe2 (L'°) 3 (Cl)] 3+), 483.5 ([Fe2 (L'°) 3] 4+), 353. 9.'H NMR ((D20) 400 MHz, 300 K): b2. 31 (3H, s, Me), 2.56 (3H, s, Me) 4. 88 (1H, dd, HPh J = 6.2 Hz, J = 2.5 Hz), 5.65 (1H, d, HpH J = 6.2 Hz, J = 2.5 Hz), 6. 55 (1H, dd, Hph J = 6.4 Hz. J = 2.5 Hz), 6.91 (1H, d, H5/6 J= 5.9 Hz), 7.14 (1H, dd, Hph J = 6.0 Hz, J = 2.4 Hz), 7.41 (1H, d, H5/6 J = 5.8 Hz), 8.44 (1H, s, H3); Selected IR data (cm-') : 3356w, 1615m, 1591m, 1490vs, 1446m, 1378m, 1311w, 1233s, 1202s, 1164m, 1104m, 1034m, 1010m, 831s, 690m, 674m.

Preparative Cellulose Column Chromatography for separation of the enantiomers. Cellulose columns were packed into 2 cm'30 cm unsintered columns using cellulose particles (-20 micron) as the stationary phase and aqueous 20 mM sodium chloride as the solvent in which the cellulose was suspended for packing. To 6 g of cellulose, 40 cm3 of 20 mM sodium chloride was added and the solution stirred to a smooth consistency. The column was packed by pouring the aqueous saline suspension of cellulose onto a glass wool pad located just above the stopcock and excess solvent was eluted. The sample, as the chloride salt (the equivalent PF6 salt is not soluble in aqueous solution), was then loaded onto the column as a saturated aqueous solution (approx. 5 mg in 1 ml) and the column eluted with 0.02 M aqueous NaCI mobile phase (compounds 1,3, 5,7, 10) or 90% MeCN (compound 9). The fractions collection was guided by visual inspection of the profile.

Preparation of L : To a stirred solution of isoquinaldaldehyde (0.314g, 2 mmol) in ethanol (30 ml) at room temperature was added dropwise an ethanolic solution of bis (4-aminophenyl) methane (0.198g, 1 mmol). After the addition was complete, the reaction mixture was stirred at room temperature for 24 hours. The resultant precipitate was filtered off, washed with ethanol and dried in vacuo under P4Olo to afford 0.33g (69%) of yellow solid.

Mass spectrum (FAB): m/z = 477 [M+H] + Elemental analysis calculated (%) for C33H24N4-0. 25H20 : C: 82.4, H: 5.1, N: 11.6 ; found: C: 82.6, H: 5.1, N: 11.6.

'H NMR (400MHz, CDC13, 298 K): 8 = 9.67 (1H, d, J = 7.7 Hz, H9), 9.09 (1H, s, H'), 8.66 (1H, d, J= 5. 8 Hz, H3), 7.90 (1H, d, J= 7.5 Hz, H6), 7.75 (3H, m, H4, H', H8), 7. 35 (4H, m, H", H"), 4. 09 (1H, s, Ho3).

IR: v= 3048 (s), 1620 (m), 1582 (m), 1550 (s), 1500 (s), 1388 (m), 1347 (m), 1312 (m), 1140 (m), 1111 (w), 1061 (w), 1011 (w), 966 (m), 905 (m), 866 (w), 847 (w), 823 (vs), 799 (m), 781 (s) 641 (s) cm-\ Coordination of L to silver (I) : Care was taken to exclude light during the following procedure. L (0.023g, 0. 05mmol) in chloroform and silver (I) hexafluorophosphate (0.012g, 0.05 mmol) in methanol were stirred for 4 hours. The yellow precipitate was collected by vacuum filtration, washed with methanol and dried in vacuo under P4Olo (0.043g, 69%). X-ray quality, pale yellow crystals were obtained by slow diffusion of benzene into a solution of the complex in acetonitrile : methanol (1: 1).

Mass spectrum (FAB) tnlz = 1312 [Ag2L2 (PF6)], 1167 [Ag2L2], 1060 [AgL2] Elemental analysis calculated (%) for [Ag2 (C33H24N4) 2] (PF6) 2-1. 5CHCl3 : C: 49.5, H: 3.0, N: 6.9 ; found: C: 49.8, H: 3.1, N: 7.0.

'H NMR (400MHz, CD3CN, 298 K): os = 9. 79 (1H, s, H'), 8.93 (1H, d, J= 8.3 Hz, H9), 8.63 (1H, d, J= 5.8 Hz, H3), 8.11 (2H, m, H4, H6), 7.93 (2H, m, H7, H8), 7.51 (2H, d, J= 8. 2 Hz, H11/12), 7.23 (2H, d, J= 8. 5 Hz, H11/12) 3. 92 (1H, s, H13).

IR: v = 3051 (w), 1612 (m), 1578 (s), 1552 (m), 1503 (s), 1427 (w), 1324 (s), 1249 (w), 1147 (m), 1018 (m), 825 (vs), 745 (s), 700 (m), 647 (m) cm-'.

Coordination of L to copper (I) : L (0.0235g, 0. 05mmol) was dissolved in chloroform and whilst stirring under a nitrogen atmosphere, [Cu (MeCN) 4] BF4 (0. 015g, 0.05 mmol) in methanol was added to give a dark violet solution. The solution was heated under reflux overnight and then cooled to room temperature. A dark violet solid precipitated from the solution and was collected by vacuum filtration, washed with methanol and dried in vacuo under P401o (0. 05g, 80%). X-ray quality, dark violet crystals were obtained by slow evaporation of the complex in acetonitrile.

Mass spectrum (FAB) tnlz = 1167 [Cu2L2 (BF4)], 1080 [Cu2L2] Positive-ion ESI (MeCN): m/z = 1167 ([Cu2L2(BF4)]+), 1015 ([CuL2]+), 540 ([Cu2L2]2+) Elemental analysis calculated (%) for [Cu2 (C33H24N4) 2] (BF4) 2-3H20 : C: 60.6, H: 4.2, N: 8. 6; found: C: 60.9, H: 3.9, N: 8. 3.

'H NMR (300MHz, CD3NO2, 298 K): os = 10.07 (1H, s, H'box), 10.67 (3H, s, H'helix) 8. 73 (4H, d, J = 8. 2 Hz, H9), 8. 42 (3H, d, J= 5.8 Hz, H3helix), 8.34 (3H, d, J= 5.0 Hz, H3box), 8.05 (4H, m, H4, H6), 7. 87 (4H, m, H', H'), 7. 58 (2H, d, J= 7.9 Hz, H11/12box), 7.44 (6H, d, J= 8.2 Hz, H""Zhelix), 7.15 (2H, d, J= 8.1 Hz, H11/12box), 7.07 (6H, d, J = 8. 4Hz, H11/12helix), 3.76 (3H, s, Hl3helix), 3.71 (1H, s, Hl3box).

IR: v = 3049 (w), 2917 (w), 1610 (w), 1581 (m), 1537 (m), 1504 (s), 1429 (m), 1401 (s), 1371 (m), 1322 (s), 1241 (w), 1199 (w), 1169 (m), 1053 (vs), 911 (m), 825 (vs), 785 (s), 747 (vs), 647 (s) cm-1.

UV-Vis (MeCN): 365 (59000), 380sh (55000), 570sh (e = 13500) nm.

Coordination of L to iron (II) : L (0.0705g, 0. 015mmol) and iron (II) tetrafluoroborate (0.034g, 0.01 mmol) in a mixture chloroform-methanol (1: 1) were stirred for 24 hours at room temperature. The blue precipitate was collected by vacuum filtration, washed with methanol and dried in vacuo under P4Olo (0. Olg, 53%). X-ray quality, blue crystals were obtained by slow diffusion of benzene into a solution of the complex in acetonitrile.

Mass spectrum (FAB) m/z = 1801 [Fe2L3 (BF4) 3], 1715 [Fe2L3 (BF4) 2], 1628 [Fe2L3 (BF4) ], 1541 [Fe2L3].

Positive-ion ESI (MeCN): m/z = 542 ([Fe2L3(BF4)]3+), 385 ([Fe2L3]4+) Elemental analysis calculated (%) for [Fe2 (C33H24N4) 3] (BF4) 4'4CH30H-3H20 : C: 59. 7, H: 4.6, N: 8. 1; found: C: 59. 6, H: 4.5, N: 8. 1.

'H NMR (400MHz, CD2CI2, 298 K): # = 9.81 (1H, s, H1), 8. 81 (1H, dd, J= 9.0, 4.2 Hz, H3). 8. 63 (1H, ddd, J= 5.2, 4.2, 1.7 Hz, H9), 8.13 (3H, m, H4, H6, H'), 7.27 (1H, broad, H"), 7.09 (1H, d, J= 6.2, Hz H'), 6. 86 (1H, broad, H"), 5.74 (1H, broad, H12), 5.54 (1H, broad, H12), 4.07 (1H, s, H13).

IR: v = 2973 (w), 1612 (m), 1579 (m), 1500 (s), 1433 (m), 1400 (m), 1365 (m), 1312 (s), 1220 (w), 1149 (m), 1049 (s), 824 (vs), 785 (s), 748 (s), 648 (s) cm-'.

UV-Vis (MeCN): 340sh (57000), 380sh (50000), 560sh (15000), 620sh (e= 28000) nm.

Preparativyi ofL and coordination to iron (II) 4, 4'-Methylenedianiline (0.059 g, 0.3 mmol) and 2-benzoylpyridine (0.110 g, 0.6 mmol) were stirred in ethanol (25 ml) for 10 minutes, two drops of glacial acetic acid were then added and the mixture was heated under reflux for 12 hours. The resulting orange solution was concentrated by rotary evaporation to produce an orange oil, which further was treated with a methanolic solution (30 mL) of iron (II) chloride tetrahydrate (0.040 g, 0.2 mmol). The mixture was heated under reflux for 72 hrs. The resulting purple solution was filtered through Celite and the filtrate concentrated to 10 mL by rotary evaporation. The complex was isolated from this solution as follows: [Fe2 (L) 3]Cl4 : A purple solid resulted when 5 mL of diethyl ether were added to the above mentioned solution. It was isolated by vacuum filtration, washed with cold methanol and dried in vacuo over P4010. Yield: 65 %. Anal. Calcd. for [Fe2 (C37H28N4) 3] Cl4. H20 : C, 71. 8 ; H, 4.7 ; N, 9.0%. Found: C, 71.9 ; H, 4.7 ; N, 8.8%.

Positive-ion ESI (MeOH): m/z 884 ([Fe2(L)3(Cl)2]2+), 578 ( [Fe2 (L) 3 (Cl)] 3+), 425 ( [Fe2 (L) 3]4+). 1H NMR (CD30D, 300 MHz, 298K): # 8.48 (1H, t, J= 6. 1 Hz, H4), 8. 18 (1H, d, J = 6.9 Hz, H6), 7. 98 (1H, t, J = 6.5 Hz, H5), 7. 38-7. 50 (5H, m, Hph), 7.23 (1H, t, J=7. 8Hz, Hph), 6.71 (1 H, d, J = 6. 7 Hz, H3), 6.11 (1 H, d, J= 7. 8 Hz, Hph), 5.99 (1H, d, J= 7.5 Hz, Hph), 4.37 (1H, d, J= 8. 1 Hz, Hph), 3.81 (1H, s, HCH2). UV-Vis (MeOH): imax [nm] (e [M-lcm-']) : 213 (212900), 281 (85200), 338 (36500), 534 (25800), 580 (35300). IR data (KBr, cm-1): 3425br, 3054w, 2958w, 2926w, 2856w, 1623s, 1598sh, 1575w, 1543w, 1502s, 1463w, 1441m, 1412vw, 1384s, 1356s, 1304w, 1259m, 1179vw, 1160w, 1106w, 1077vw, 1019m, 1000w, 924vw, 821w, 796w, 742m, 700s, 665vw, 649vw, 617w, 604w, 556vw, 540vw, 419w, 403w.

Further details of methods for manufacturing ligands for use in the production of supramolecular compounds which may be used in the claimed invention are shown in the following papers: Readily prepared metallo-supramolecular triple-helicates designed to exhibit spin-crossover behaviour F. Tuna, M. R. Lees, G. J. Clarkson and M. J. Hannon, Chem. Eur. J. , 2004, Using non-covalent intra-strand and inter-strand interactions to prescribe helix formation within a metallo-supramolecular system L. J. Childs, M. Pascu, A. J. Clarke, N. W. Alcock and M. J. Hannon, Chem. Eur. J. , 2004, 10, 4291-4300 Binding sites on the outside of metallo-supramolecular architectures; engineering coordination polymers from discrete architectures M. Pascu, F. Tuna, E. Kolodziejczyk, G. I. Pascu, G. Clarkson and M. J. Hannon., Dalton Trans., 2004, 1546-1555 Aggregation of metallo-supramolecular architectures by metallo-assembled hydrogen bonding sites.

A. Lavalette, F. Tuna, J. Hamblin, A. Jackson, G. Clarkson, N. W. Alcock and M. J. Hannon, Chem. Commun. , 2003,2666-2667 Metallo-supramolecular libaries: triangles, polymers and double-helicates assembled by copper (I) coordination to directly linked bis-pyridylimine ligands.

F. Tuna, J. Hamblin, A. Jackson, G. Clarkson, N. W. Alcock and M. J. Hannon, Dalton Trans., 2003,2141-8.

The effect of phenyl substituents on supramolecular assemblies containing directly linked bis-pyridylimine ligands: synthesis and structural characterisation of mononuclear nickel (II) and dinuclear silver (I) and cobalt (III) complexes of (2-pyridyl) phenylketazine.

F. Tuna, G. Clarkson, N. W. Alcock and M. J. Hannon, Dalton Trans., 2003, 2149-55.

Interfacing supramolecular and macromolecular chemistry: Metallo-supramolecular triple-helicates incorporated into polymer networks.

A. Lavalette, J. Hamblin, A. Marsh, D. M. Haddleton and M. J. Hannon, Chem.

Commun., 2002,3040-3041.

Assembly of a nanoscale chiral ball through supramolecular aggregation of bowl-shaped triangular helicates.

L. J. Childs, N. W. Alcock and M. J. Hannon, Angew. Chem., liztl. Ed., 2002, 41, 4244-4247.

Helical (Isotactic) and Syndiotactic Silver (I) Metallo-Supramolecular Coordination Polymers assembled from a readily-prepared Bis-Pyridylimine Ligand containing a 1,5-Naphthalene Spacer.

F. Tuna, J. Hamblin, G. Clarkson, W. Errington, N. W. Alcock and M. J. Hannon, Chem., Eur. J., 2002, 8, 4957-4964.

Triple helicates and planar dimers arising from silver (I) coordination to directly linked bis-pyridylimine ligands.

J. Hamblin, A. Jackson, N. W. Alcock and M. J. Hannon, J. Chem. Soc., Dalton Trans., 2002, 1635-1641.

Directed one-pot syntheses of enantiopure dinuclear silver (I) and copper (I) metallo-supramolecular double helicates.

J. Hamblin, L. J. Childs, N. W. Alcock and M. J. Hannon, J. Chem. Soc., Dalton Trans., 2002,164-169.

Paper: a cheap yet effective chiral stationary phase for chromatographic resolution of metallo-supramolecular helicates.

M. J. Hannon, 1. Meistermann, C. J. Isaac, C. Blomme, J. R. Aldrich-Wright and A.

Rodger, Chem. Commun., 2001,1078-1079.

Assembly of nano-scale circular supramolecular arrays through 7V-7t aggregation of arc-shaped helicate units.

L. J. Childs, N. W. Alcock and M. J. Hannon, Angew. Chem., Intl. Ed., 2001, 40, 1079-1081.

A metallo-supramolecular double helix containing a major and a minor groove.

M. J. Hannon, C. L. Painting and N. W. Alcock, Chem. Commun., 1999,2023-4.

Spacer control of directionality in supramolecular helicates using an inexpensive approach.

M. J. Hannon, S. Bunce, A. J. Clarke and N. W. Alcock, Angew. Chem., Intl. Ed., 1999, 38, 1277-8.

An inexpensive approach to supramolecular architecture.

M. J. Hannon, C. L. Painting, J. Hamblin, A. Jackson and W. Errington, Chem.

Commun., 1997, 1807-1808.

Chiral supramolecular arrays may be produced as shown in J. Hamblin, L. J. Childs, N. W. Alcock and M. J. Hannon, J. Chem. Soc., Dalton Trans., 2002, 164-169 and Chem. Commun., 2001,1078-1079 Spacer Control of Directionality in Supramolecular helicates is shown in Angew.

Chem. Int. Ed. 1999,38, No. 9,1277-8.

Polymeric Helical and Helical arrays may be produced as shown in a paper F. Tuna, J.

Hamblin, G. Clarkson, W. Errington, N. W. Alcock and M. J. Hannon, Chem., Eur. J. , 2002, 8, 4957-4964.

The supramolecular compounds produced may be purified by chromatographic resolutions, see Chem. Commun. , 2001, 1078-1079. In the process, paper chromatographic or cellulose chromoatography using saline solution as an element affords the two enantiomers.

Further synthetic examples Synthesis of ligand L3 H /-. - N N O I iN N/O xNsH N 0 N N1 0 O O O O non ethylene glycol "OMSon. p. t. S : , YOH (aq) eOH 0 DMSO/Iz p-toluenesulfonic acid "NaOH (aq)/MeOH O I iN-'O I N'-' I iN ^ O iN 960 C reflux toluene /Q/p/p Na+'O 6-Formyl-nicotinic acid methyl ester. 6-Methyl-nicotinic acid methyl ester (5.00 g, 33.1 mmol) was mixed with iodine (8.40 g, 33.1 mmol) and a small amount of DMSO was added to promote mixing. After addition of DMSO (Sml), this solution of added to a heated solution of DMSO (15 ml) at 130°C. The temperature of the mixture is then slowly raised to 160°C and stirred at this temperature for 15 minutes. After cooling down the solution, a small amount of a saturated aqueous solution of Na2CO3 is added.

Extraction of the product with diethyl ether. Crude compound used without further purification.

'H NMR (400 MHz, CDC13, 298K) 5 10.00 (s, 1H, CHO), 9.22 (d, 3J (H, H) =1. 5 Hz, 1 H, ArH), 8.34 (dd, 3J (H, H) =6. OHz ; 2.0 Hz, 1 H, ArH), 7.90 (d, 3J (H, H) =8. 0 Hz, 1 H, ArH), 3.87 (s, 3 H, CH3).

6- 1, 3] Dioxolan-2-yl-nicotinic acid methyl ester. 6-Formyl-nicotinic acid methyl ester (300 mg, 1. 82 mmol) was dissolved in toluene (25 ml) and ethylene glycol (0.33 ml, 5.92 mmol) and p-toluenesulfonic acid (cat) were added. The mixture is refluxed with a dean-stark for 7.5 hours. The solvents are evaporated and the crude product was purified by column chromatography (Si02, CH2Cl2/MeOH =99/1). The protected aldehyde was obtained as a white solid (310 mg, 81%).

'H NMR (400 MHz, CDC13, 298K) 8 9. 18 (d, 3J (H, H) =1.8 Hz, 1 H, ArH), 8.31 (dd, 3J (H, H) =8.2Hz ; 2. 2 Hz, 1 H, ArH), 7.59 (d, 3J (H, H) =8. 0 Hz, 1 H, ArH), 5.87 (s, 1H, CH), 4.16-4. 05 (m, 4 H, CH2), 3.93 (s, 3 H, CH3)."C NMR (100 MHz, CDC13, 298K) 8 165.5 (C=O), 161.0 (ArC), 150.5 (ArCH), 138.0 (ArCH), 126.2 (ArC), 120.3 (ArCH), 103.1 (CH), 65.7 (CH2), 52.5 (CH3).

6- [1, 3] dioxolan-2-yl-nicotinate sodium salt. 6- [1, 3] Dioxolan-2-yl-nicotinic acid methyl ester (78 mg, 0.38 mmol) was dissolved in MeOH (1 ml) and an 1M aqueous solution of NaOH (1 ml) was added while the mixture was kept in a water bath. The mixture was stirred for 2 hours at room temperature before the solution was evaporated to dryness. The crude was used without further purification.

'H NMR (400 MHz, D20, 298K) 8 8.93 (d, 3J (H, H) =2.0 Hz, 1 H, ArH), 8.29 (dd, 3J (H, H) =8. 2Hz; 2.2 Hz, 1 H, ArH), 7.67 (d, 3J(H, H) =8.0 Hz, 1 H, ArH), 5.92 (s, 1H, CH), 4.20-4. 13 (m, 4 H, CH2). N-a-benzyl-glycine. Glycine (1. 88 g, 25 mmol) and p-toluenesufonic acid (4.65 g, 25.5 mmol) were added to a solution of benzyl alcohol (10 ml) in toluene (35 ml). The mixture was refluxed with a dean-stark for 3 h and cooled to room temperature. Diethyl ether (25 ml) was added and the mixture was cooled in an ice-bath. The white precipitate was filtered and washed with diethyl ether. Crude as p-TsOH salt is used without further purification.

'H NMR (400 MHz, D20, 298K) 8 7.66 (d, 3J (H, H) =8. 3 Hz, 2 H, ArH), 7.42 (s, 5 H, Ph), 7.33 (d, 3J (H, H) =8.0 Hz, 2 H, ArH) 5.27 (s, 2 H, CH2), 3.92 (s, 2 H, CH2), 2.36 (s, 3 H, CHs).

Compound 1. 6- [1, 3] dioxolan-2-yl-nicotinate sodium salt (80 mg, 0.42 mmol) was suspended in acetonitrile (5 ml) and a suspension of glycine in acetronitrile (10 ml) was added. HBTU (180 mg, 0.50 mmol) and DIPEA (0.36 ml, 2.08 mmol) were added to the mixture. The mixture is stirred for 1 hour before the white solid is filtered off.

Evaparation of the solvent gave yellow oil, which was dissolved in CH2C12 (5 ml) and washed with Hz0 (two times). The organic layer was dried on MgSO4 and evaporated to dryness. The yellow oil was purified by column chromatography (Si02, CH2Cl2/MeOH =99/1 followed by CH2Cl2/MeOH =98/2). The protected aldehyde was obtained as a white solid (66 mg, 48 %).

'H NMR (400 MHz, CDCL3, 298K) 8 9.00 (d, 3J (H, H) =2.1 Hz, 1 H, ArH), 8. 18 (dd, 3J@ (H, H) =8.1 Hz; 2.1 Hz, 1 H, ArH), 7.63 (d, 3J (H, H) =8.1 Hz, 1 H, ArH), 7.36 (s, 5H, Ph), 6. 78 (br s, 1H, NH), 5.89 (s, 1H, CH), 5.22 (s, 2H, CH2), 4.29 (d, 3J (H, H) =5.1 Hz, 2 H, CH2), 4.18-4. 03 (m, 4 H, CH2).

Compound 2. Compound 1 (100 mg, ) was dissolved in a mixture of acetone (19 ml) and H20 (2 ml) and p-TsOH (200 mg, ) was added. The mixture was refluxed overnight and the solvents were evaporated. The solid is redissolved in CH2Cl2 and washed with H20 (3 times). The compound is obtained as a white solid (60 mg,) 'H NMR (400 MHz, CDC13, 298K) 8 10.02 (s, 1 H, CHO), 9.12 (d, V (H, H) =1. 5 Hz, 1 H, ArH), 8.23 (dd, 3J (H, H) =8. 0 Hz; 2.0 Hz, 1 H, ArH), 7.91 (d, 3J (H, H) =7.6 Hz, 1 H, ArH), 7.37 (d, 3J (H, H) =5. 0 Hz, 1 H, NH), 7.30-7. 17 (m, 5 H, Ph), 5.22 (s, 2 H, CH2), 4.20 (d, 3J (H, H) =5.3 Hz, 2 H, CH2).

Compound 3 (ligand L2) Compound 2 (39 mg, 0.13 mmol) and 4,4'-methylene dianiline (10 mg, 0.050 mmol) were dissolved in ethanol (10 ml) and the mixture was stirred for 1 hour. The ligand was obtained by filtration as an off-white solid.

'H NMR (300 MHz, DMSO-d6, 298K) 8 9.35 (s, 1 H, NH), 9.14 (s, 1 H, ArH/CH), 8. 68 (s, 1 H, ArH/CH), 8.36 (d, 3J@ (H, H) =10.2 Hz, 1 H, ArH), 8.26 (d, 3J (H, H) =7.9 Hz, 1 H, ArH), 7.41-7. 30 (m, 9 H, Ph; ArH), 5.18 (s, 2 H, CH2), 4.14-4. 03 (m, 4 H, CH2).

[Cu2L22] Cl2. Ligand L2 (4.0 mg, ) was suspended in MeOD-d4 (0.50 ml) and CuCl (0.5 mg, 0.005 mg) in MeOD-d4 (0.5 ml) was added. The resulting pink mixture was stirred for 0.5 hour.

'H NMR (400 MHz, MeOD-d4, 298K) S 9.47 (s, 1 H, Ar/CH), 9.03 (s, 1 H, ArH/CH), 8. 65 (d, 3J (H, H) =6.5 Hz, 1 H, ArH), 8.30 (d, 3J (H, H) =8. 3 Hz, 1 H, ArH), 7.50-7. 21 (m, 10 H, Ph; ArH; NH), 5.21 (s, 2 H, CH2), 4.63 (d, 3J (H, H) =4.6 Hz, 2 H, CH2), 4.20 (s, 2 H, CH2).

Ligand L' Ligand L1. 6-Formyl-nicotinic acid methyl ester (30 mg, 0. 18 mmol) and 4, 4'-methylene dianiline (17 mg, 0.086 mmol) were dissolved in ethanol (10 ml) and the mixture was stirred for 3 hours. The ligand was obtained by filtration as a white-yellow solid (33 mg, %). FAB-MS Calcd for C29H24N40YYm/z= 492. 2, Found mlz =493. 1 [M=H].

'H NMR (400 MHz, CDC13, 298K) 8 9.28 (d, 1H, 3J (H, H) =1.5 Hz ArH), 8.67 (s, 1H, CH), 8.39 (d, 3J (H, H) =8. 3 Hz; 2.0 Hz, 1 H, ArH), 8. 28 (d, 3J (H, H) =7.8 Hz, 1 H, ArH), 7.30-7. 22 (m, 4H, ArH), 4.05 (s, 1H, CH2), 3. 98 (s, 3H, CH3).

[Cu2lA] Cl2. Ligand L' (10 mg, 0.020 mmol) was suspended in MeOH (10 ml) and CuCl (2 mg, 0.020 mg) in MeOH (5 ml) was added. The mixture was stirred for 2 hours at room temperature followed by 4 hours at 65 °C. Solution was cooled down and filtered through cotton wool. Evaporation gave the crude complex as a dark red solid.

'H NMR (400 MHz, CDC13, 298K) 8 9.31 (s, 1H, ArH), 9.24 (s, 1H, CH), 8.65 (d, 3J (H, H) =8.0 Hz, 1 H, ArH), 8.47 (d, 3J (H, H) =8.0 Hz, 1 H, ArH), 7.41 (d, 3J (H, H) =7.8 Hz, 1 H, ArH), 7.21 (d, 3J (H, H) =7.8 Hz, 1 H, ArH), 3.95 (s, 1H, CH2), 3.90 (s, 3H, CH3).

[Ag2L] Cl2. Ligand L' (20 mg, 0.041 mmol) was suspended in MeOH (15 ml) and Ag (acetate) (6. 8 mg, 0.041 mg) in MeOH (5 ml) was added. The mixture was refluxed for 3 hours, followed by filtration over celite. Metanolic ammonium hexafluorophosphate was added, the resulting yellow precipitate was collected by vacuum filtration (5.8 mg, 19 %) 'H NMR (400 MHz, CDC13, 298K) 8 9.28 (d, 3J (H, H) =2.0 Hz, 1 H, ArH), 8. 97 (s, 1 H, CH), 8. 62 (dd, 3J (H, H) =8.0 Hz; 2. 0 Hz, 1 H, ArH), 8.14 (d, 3J (H, H) =8. 0 Hz, 1 H, ArH), 7.43 (d, 3J (H, H) =8. 3 Hz, 1 H, ArH), 7.31 (d, 3J (H, H) =8.3 Hz, 1 H, ArH), 4.02 (s, 1H, CH2), 3. 98 (s, 3H, CH3).

Treatment of Cancer Cells As stated above, the cationic, metal ion assembled, supramolecular architectures (including but not limited to bi-and poly-metallo-double-and triple-helicates) may be used as agents for anti-tumour and anti-viral treatment alone or in combination with biomolecules or synthetic agents.

Cell line testings were carried out on human ovarian cancerous cells (A2780 normal and A2780 cisplatin resistant cells) These are available from European Collection of Cell Cultures (ECACC) -ECACC 93112517 and ECACC 93112519. The cisplatin resistant cell line is also cross resistant to melphan, adriamycin and irradiation, but is a useful model because of its resistance to cisplatin. The Compound tested was that disclosed in Meistermann et al. (PNAS 2002,99. Pages 5096-5074).

Cell survival was evaluated using a system based on the tetrazolium compound MTT, which is reduced by living cells to a formzan product that can be detected colourimetrically at 520nm. Cells were plated at a density of 4000 cells/well in sterile 96-well plates in 200, ul of media and allowed to attach overnight. The media was removed and replaced with media containing final concentrations from 0 to 1 mM.

Seventy-two hours later, 20, ul of a fresh MTT solution in PBS at a concentration of 1 mg/ml was added to the cells and the plate incubated for 4h at 37°C in a humidified atmosphere of 5% C02 where purple crystals of the formazan product were produced.

The media was removed carefully by aspiration and 25 ul of Sorenson Buffer (0. 1M gylcine, 0. 1M NaCl, 0. 1M NaOH, pH 10.5) and ZOO, ul of DMSO were added to lyse the cells and dissolve the formazan product, respectively. The absorbance was measured at 520nm. Curves constructed from a plot of (%) cell survival versus drug concentration were used to determine the ICso (compound concentration required to produced 50% cell growth inhibition).

Results using supramolecular agent racemic [Fe2 (C2sH2oN4) 3] Cl4 : A2780 IC50 =8, uM A2780 cisplatin resistant IC50 =190, uM using supramolecular agent (-)- [Fez (C2sH2oN4) 3] Cl4 : A2780 IC50 =20, uM A2780 cisplatin resistant IC50 =89, uM using supramolecular agent (+)- [Fe2 (C25H2oN4) 3 C14 : A2780 IC50=13, uM A2780 cisplatin resistant IC50 =36, uM Further cancer cell lines HBL-100 (epithelial breast cancer) and T47D (epithelial ductal carcinoma of the breast) cells were cultured in RPMI (Roswell Park Memorial Institute) 1640 media, supplemented with FCS (10 %), L-glutamine (1%), non-essential amino acids (1%), sodium pyruvate (1%), antibiotic/antimycotic (1%) and HEPES (1%) in an atmosphere of 95% air and 5% C02 at 37°C.

HBL-100 ICso = 1.3 micromolar +/-0. 05 micromolar T47D ICso = 4.2 micromolar +/-1. 0 micromolar Protein Synthesis Assay General 96well flat bottomed plates were obtained from Nuclon (Gibco-BRL, Glasgow, UK). FBS (foetal calf serum) and DMEM (Dulbeccos modified Eagle's medium) was from Gibco (Glasgow, UK). 35S-methionine, non-essential amino acids, L-glutamine, sodium pyruvate, HEPES (4- (2-hydroxyethyl)-1-piperazineethanesulfonic acid), antibiotic/antimycotic suspension were obtained from Sigma (Poole, UK).

Scinillation fluid was obtained from Fisher (Loughborough, UK).

Cell Culture Conditions HeLa (epitheloid carcinoma of the cervix) cells were cultured in DMEM, supplemented with FCS (10 %), L-glutamine (1%), non-essential amino acids (1%), sodium pyruvate (1%), antibiotic/antimycotic (1%) and HEPES (1%) in an atmosphere of 95% air and 5% C02 at 37°C.

Protein Synthesis Assay Protein synthesis was determined using a 35S-methionine incorporation assay. HeLa cells were seeded at a density of 104 cells/well in 200, ul of medium and were allowed to attach overnight. The Iron triple helicate [Fe2 (C2sH2oN4) 3] cl4 was added to final concentrations 0-1 mM in a volume of 200 µl media per well. Twenty-four hours later, the media was removed and the plates washed twice with PBS (phosphate buffered saline). To each well was added one curie of 3sS-methionine in 100 ml of media and the cells incubated for 1 hour at 37°C in a humidified atmosphere of 5% CO2. The radioactivity was removed and the cells treated with trifluroacetic acid to precipitate proteins and the plates washed 3x with PBS.

Scintillation fluid (100, ut) was added to each well and incorporated radioactivity counted using a scintillation counting performed using a direct counting method.

Results were standardised according to 35S-methionine incorporation/104 cells to standardize results to cell number Results IPso (Inhibition of 50% of protein synthesis) = 118 mM Experiment to confirm the anti-bacterial growth effects of a supramolecular agent The growth rate of Synechocystis sp PCC 6803 was assessed in the presence of varying concentrations of the purple supramolecular agent [Fe2 (C2sH2oN4) 3] Cl4 (0-10. 1mM).

Synechocystis sp. PCC 6803 cultures were grown in 20ml BGII medium contained in 50ml conical flasks and at constant illumination of 30 microEinsteins m-'sec-. Cell density was measured at 750nm using uninnoculated BG11 media as a blank. The cells stain visibly purple at 1, uM and cell growth is stopped above this concentration.

The results are shown in Figure 4 RNA binding experiment Compounds of the invention have also unexpectedly been found to bind to RNA, thus indicating an alternative mode of action of the compounds Circular dichroism (CD) spectra were collected in 1 cmpathlength cuvettes using a Jasco J-715 spectropolarimeter. Spectroscopic titrations were performed in which CD and UV/Vis absorbance spectra were collected. Titrations were carried out using supramolecular agents [Fe2(C25H20N4)3]Cl4 or [Fe2(C21H18N6)3]Cl4 and conducted at constant concentrations of Poly (G) -poly (C) RNA (300, uM), NaCl (20 mM) and sodium cacodylate buffer (1 mM). The RNA: supramolecular agent ratio was varied during the titration series while retaining constant RNA concentration and incrementing the concentration of supramolecular agent in the cuvette from 0-38, uM. In both cases induced CD signals appeared in the MLCT region of the supramolecular agents at -550nm for [Fe2 (C2sH2oN4) 3] Cl4 and between 450-600nm for [Fe2 (C2lHz8N6) 3] C14. The appearance of these bands confirms binding of the supramolecular agent to the RNA.

This lead compound used in the toxicity, antibacterial and protein synthesis study is a tetracationic cylinder and forms a triple helicate. Similar structures with substitutions are expected to have similar properties. Many of structures described above have similar dimensions, cationic properties, metal binding sites etc. and are also expected to have such properties.