DESCRIPTION Technical field The present invention relates to new macrocyclic systems of porphyrazine-type and their metal derivatives, characterized by the presence of heteroatoms at the periphery of the macrocyclic ring.

This new series of compounds of porphyrazine-type supplement the class of compounds so called "phthalocyanines" ("The Phthalocyanines", F. H. Moser, A. L. Thomas, Eds.; CRC Press, Boca Raton, Florida, Vol. 1 and II, 1983), comprising the phthalocyanine and the metal derivatives thereof, already known since the 1930s (R. P. Linstead and al., J. Chem. Soc., 1936,1016, and later works), as laboratory synthetic products and having a molecular structure bringing to mind that of analogue synthetic and natural porphyrines ("The porphyrines", D.

Dolphin, Ed.; Acad. Press Inc.; New York; Vols. I-VII (1979)).

Background Art It is well known from the last 50 years literature that the phthalocyanines as such and as the derivatives thereof having various substituents on the peripheral benzene rings, have been the object of a large interest both in basic researches and for researches of applicative type ("Phthalocyanines: Properties and Applications", C. C. Leznoff, A. B. P. Lever, Eds., VCH Publ., New York, Vols. I-IV (1989-1996). They are intensively studied as special materials for forming thin films, for applications in the fields of sensors, electric conductivity and semiconductivity, electrochromics, liquid crystals, catalysis, non-linear optic properties, graphic reproduction, but also for practical interest aspects, such as the preparation of inks and dyes for textiles, to mention only some among those of present major interest. It ensues that the

phthalocyanines are manufactured and put into the market by big chemical industries and by industries specialized in research purposes, among which Carlo Erba, Aldrich (U. S. A.) and Fluka (Germany).

Valid alternatives do not seem to have resulted from attempts made in the last years to supplement the pthalocyanines with new classes of compounds, similar in molecular and electronical structure, but having innovative elements such as to allow an equal broad utilization in the development of basic research and new specialistic applications.

Disclosure of the invention The new phthalocyanine-like systems, according to the present invention, open the possibility of new scientific investigations, with potential capabilities of broader technological applications in fields of great importance both for the basic research and industrial field utilization.

Object of the present invention are macrocyclic porphyrazine-type compounds and the metal derivatives thereof, characterized by the fact of comprising rings of heterocycle type at the periphery of the inner porphirazine fragment.

The new macrocyclic compounds according to the present invention can have, at the periphery of the inner porphyrazine fragment, rings of heterocycle type, i. e. thiadazole or selenodiazole type, and they show the following structural formula (1)

in which X can be selected from the group comprising S and Se.

A further object of the present invention are the metal derivatives of the above mentioned molecules.

Hereinafter the molecule according to the invention with the thiadiazole ring and the metal derivatives thereof will be also indicated as I-a, whereas the molecule with selenodiazole ring and the metal derivatives thereof will be also indicated as I-b.

An additional object of the present invention is a process for the preparation of the macrocyclic compounds (1) and the metal derivatives thereof, characterized by cyclotetramerizating the monomers 5- thiadiazole, or 5-selenodiazole, with metallorganic or inorganic salts, in organic solvents, eventual extraction of the metal by treatment with strong acids from the formed complexes to obtain tetra (thiadazole) porphyrazine, or tetra (selenediazolo) porphyrazine, and eventual treatment of these compounds by a metallorganic or inorganic salt to obtain the metal derivatives thereof different from the previously extracted metals.

Detailed description of the invention In the process according the present invention, the inorganic salt used for the cyclotetramerization can be a salt of a metal selected from the group comprising Mg (II), Al (III), Ga (III) and In (III). The extraction of the metal from the formed complexes can be obtained with strong acids selected from the group comprising acetic acid, trifluoroacetic acid and sulphuric acid.

In a particular embodiment of the present invention, the preparation of a specific compound of formula (1) and, from that, of a series of metal derivatives, is carried out starting from monomer species comprising 3,4- dicyano-1,2,5-thiadiazole (DCTD) and from the corresponding selenium monomer (DCSeD), obtained from commercially available (Carlo Erba, Aldrich, Fluka) diaminomaleodinitryl (DAMN), and thionyl chloride respectively (yield 80-90%), following a process already described in the literature (G. Ribaldone, R. Grecu, Germ. Pat. 2651604 (1977), Chem.

Abst., 87,1977,135344) and Se02. For DCSeD, the same reagents (DAMN and Se02) have been used by Shew (D. Shew, Diss. Abstr., 20,1959,1593; Chem. Abstr. 54,4548a). We have observed that by stirring DAMN with Se02 in CH2C12, DCSeD was obtained with a practically theoretical yield (97-100%). Some authors instead prepared DCSeD from diiminosuccinonitryl and Se02, but with a lower yield (H. W. Roesky, T. Gries, H. Hofman, J. Schimkowiak, P. G.

Jones, K. Meyer-Base, G. M. Sheldrik, Chem. Ber., 119, 1986,366).

The process of cyclotetramerization of the monomers DCTD and DCSeD can be operated by reaction with Mg (II) as a template in alkoxylate form (such as propoxylate, butoxylate), in the presence of small amounts of Iz as a catalyst. The metal can be extracted from the Mg (II) complex by treatment with strong acids (CH3COOOH, CF3COOH, H2SO4) to obtain the compound (1). The preparation of other metal derivatives can proceed from the compound (1) by selecting a new metal respectively in form of an organic or inorganic salt (such as acetate, chloride, sulphate and the like) and under suitable conditions of temperature and reaction means (dimethylsulphoxide, pyridine, quinoline, y-picoline and

the like). The reaction sequence, starting from DCTD, has the schema outlined as follows: DCTD + Mg (OC3H7) 2-+ TTDPzMg. (solv.) TTDPzMg. (solv.) - TTDPzH2. (solv.) TTDPzH2.(solv.) + M (II)-+ TTDPzM. (solv.) (py, DMSO) A similar schema applies to the case of DCSeD.

The new macrocyclic compounds according to the invention show in common with the phtalocyanine class: a) the central porphyrazine fragment; b) the substantially square, planar structure of the whole macrocycle compound, in view of the peculiar structural characteristics of the thiadiazole and selenodiazole <BR> <BR> <BR> <BR> <BR> rings; c) wide delocalization of n electrons which, similarly to phthalocyanines, extend throughout the molecular system. It is to be noted that, as in the thiadiazole and selenodiazole rings the number of7t electrons is the same as that in the benzene ring, the new molecular systems provided in the present invention are isoelectronic to the phthalocyanines under this aspect.

The basic and interesting feature distinguishing the compounds described in the present invention from the phthalocyanine class resides in the presence of heteroatoms (N, S, Se) at the periphery of the macrocyclic ring. The spectroscopic behaviour in the visible UV region of the new systems shows that such presence produces differentiation features in the <BR> <BR> <BR> <BR> distribution of the z electron charge inside the molecular system of the macrocycles. In addition, the S and Se atoms, having"soft"atom characteristics, represent a strong novelty item. In fact they necessarily produce a peculiar situation of the contacts of one molecule to the other in the solid state. This has been shown to be of extreme importance in the field of the phthalocyanines as materials having, to say, electric conductivity properties, as such or after undergoing an

oxidative doping. The additional advantageous property of the new class of macrocycle compounds is the general tendency thereof to attract molecules or metal ions at the periphery of the macrocycle ring essentially in view of the presence of the nitrogen atoms. For instance both of the macrocycle ligands of formula (1), and the respective metal derivatives are generally obtained in the air in the form of hydrates as a consequence of an engagement of H20 molecules at the macrocycle periphery.

In addition this has influence on the solid state or of any other nature crystal, and on the possible interactions between the macrocycles in the solid state itself.

Herein before a general description of the invention has been presented. A more detailed description of specific embodiments will be given hereinafter with reference to the following examples, aiming at enhancing the objects, features and advantages of the invention. In particular the examples show some methods concerning the derivatives containing the thiadiazole ligand. Similar methods also apply to the corresponding products containing selenium.

EXAMPLE 1 Preparation of [TTDPzMg (H20)]. CH3COOH The hydrated Mg (II) Tetra (thiadiazolo) porphyrazinate is prepared according to the following method.

Mg Grignard scrapings (750 mg; 30,8 mmols) activated with Hcl 1 N, n-propyl alcohol previously distilled on CaO or Na (30 ml), a few I2 crystals having catalyst function, are introduced in a 100 ml two-necks flask. The flask is provided with a bubble cooler having a CaCl2 pipe at its upper end and the reaction mixture is boiled for 19 hours. The DCTD (4,22 G; 30 mmols) is added to the reaction mixture and it is refluxed for additional 16 hours. After cooling and removing the propanol, the solid is washed with CH2Cl2 to remove the unreacted DCTD. Then the solid is suspended under stirring for one hour in 50%

CH3COOH for separation of excess magnesium propylate. The suspension is filtered and the separated solid is washed with water to neutrality and dried under vacuum (1,95 g; yield about 45%). The so obtained complex corresponds to formula [TTDPzMg (H20)]. (CH3COOH). The content of H20-and CH3COOH slightly varies from sample to sample.

EXAMPLE 2 Preparation of the macrocylic ligand (1) containing S [TTDPzH2] The solvated magnesium complex (1,95 g; about 3,42 mmols) is introduced into a 50 ml one-neck flask containing 10 ml CF3COOH. The violet coloured suspension is boiled for 2 hours. 10 ml of water are cautiously added and it is refluxed for additional 20 minutes. After cooling the solid is separated by centrifugation, washed from the washings with water to neutrality and brought to constant weight under vacuum. A purple coloured powder (412 mg; yield 21,3%) is obtained, corresponding to TTDPzH2 containing small amounts of carboxylic acid and H20, varying slightly from preparation to preparation.

The solvated compound can be heat-sublimated under vacuum (400-450 C°, 10-2 mmHg) to obtain TTDPzH2.

EXAMPLE 3 Preparation of TTDPzCu This complex can be prepared from the corresponding Mg (II) solvated complex and copper acetate (in excess) in trifluoroacetic acid by refluxing the mixture for 14 hours, successive addition of H20 (with caution) and further heating for 15-30 minutes, to which follows a heat treatment (300 C°) under vacuum (10-2 mmHg) for 1 hour of the solid so separated (yield 45-50%). The complex can also be obtained by a reaction at room temperature of solvated TTDPzH2 and copper acetate (in excess) in pyridine, maintaining the mixture under stirring for 24 hours, and following separation, washing with ethanole and treatment under vacuum of the so obtained solid (yield 60%).

The Mg (II) and Cu (II) complexes of the class I-a have been illustrated in the prior art with preparation methods different from the ones herein before described.

These methods, however, involve a difficult purification of the isolated materials, show elemental analysis data of unreliable interpretation and provide, at least in one case (Mg (II)), extremely low yields (E. H. Mrkved, S. M.

Neset, H. Kjsen, G. Hvistandahl, F. Mo, Acta Chem.

Scand., 1994,48,912).

As to the macrocyclic ligand containing Se (TSeDPzH2), and the Mg (II) and Cu (II) derivatives thereof, belonging to the class I-b, the synthesis methods are similar to those referenced as to the corresponding thiadiazole species, with variations only with respect to the additioned molecules (H2O, carboxylic acid).

The preparation methods of the metal derivatives of the sulphur-containing macrocycle (TTDPzH2) described herein below, apply to non-critical experimental conditions and most of the compounds so obtained are stable in air. The complexes can hold in some cases molecules of the solvent medium which are coordinated to the central metal (py, DMSO), and in all cases H20 molecules weakly linked to the peripheral part of the molecule.

The so prepared complexes correspond to general formulas of the kind: <BR> <BR> <BR> <BR> <BR> 1) [TTDPzM (py) 2] (H20) x (M = Mn (II), Fe (II), Co (II), Ni (II) ;<BR> <BR> <BR> <BR> <BR> <BR> x-2)<BR> <BR> <BR> <BR> <BR> <BR> <BR> 2) [TTDPzM (DMSO) 2] (DMSO) x (M = Mn (II), Fe (II); x = 0-1) 3) [TTDPzM] (H20) x (generalmente x-2) (M = Mn (II), Fe (II), Co (II), Ni (II), Zn (II)); 4) [TTDPzM] (M = Mn (II), Fe (II), Co (II), Ni (II), Zn (II) 5) [TTDPzM (X)] (H20) x (M = Al (III), Ga (III), In (III); X = Cl, Br; x-= 2) Composition variations, as far as similar complexes derived from TSeDPzH2 are concerned, are observed only in

relation to the nature and the number of neutral molecules added (H2O, carboxylic acid, DMSO, Py).

EXAMPLE 4 The compounds of class 1) are obtained using pyridine as a reaction medium, inert environment (Fe, Mn), boiling temperature of the solvent, reaction time of 1-3 hours, with yields higher than 80-85%. Aa an example the method is illustrated for the species [TTDPzFe (Py) 2] (H20) x (x-2).

In a 50 ml two-necks flask pyridine is degassed under N2 current for 5 minutes and, under N2 current, Mohr salt (300 mg; 0,75 mmols) and TTDPzH2 (248 mg; about 0,45 mmols). are added. The mixture is refluxed in an N2 atmosphere for 5 hours. After cooling, the solid product is separated by centrifugation, washed with water to remove the remaining Mohr salt in excess, and brought to constant weight under vacuum (300 mg; yield about 83%).

EXAMPLE 5 The compounds of class 2) are obtained using the DMSO as a reaction medium, inert environment, temperature of about 200 C°, reaction time of 3 hours, with yields higher than 80-85%. The synthesis method is reported with reference to the complex TTDPzFe (DMSO) 2: In a 50 ml two-necks flask are introduced, under N2 current, freshly distilled DMSO (20 ml), Mohr salt (348 mg; 0.89 mmols) and solvated TTDPzH2 (271,8 mg; about 0,50 mmols). The mixture is brought to a temperature of 200 C° and it is maintained under stirring for 3 hours in inert environment. After cooling the reaction mixture is centrifugated, and the dark green solid is washed several times with H20 to remove the Mohr salt in excess and it is brought to constant weight under vacuum (320 mg; yield about 85%).

EXAMPLE 6 Interconversion of the species belonging to the classes 1) and 2). As an example reference is made to the Fe (II) case: [TTDPzFe (py) 2] (H20) 2 and [TTDPzFe (DMSO) 2].

Complex [TTDPzFe (py) 2] (H20) 2 can be trasformed into an analogue thereof containing DMSO by refluxing the starting complex in anhydrous and freshly distilled DMSO for 2-3 hours. The inverse reaction (DMSO- py, H20) is brought about by heat-boiling a complex suspension containing DMSO in pyridine for about 2 hours.

EXAMPLE 7 The compounds of class 3), with the exclusion of those containing Fe (II) and Mn (II), are obtained directly from TTDPzH2 and an excess of the metal salt, by refluxing the reaction mixture for 2-3 hours in DMSO (or even in pyridine in the case of Cu (II) and Zn (II)). The Fe (II) and Mn (II) complexes are obtained from the corresponding complexes of classes 1) and 2) by heat treatment (300 C°) under vacuum (10-2 mmHg) for 1-2 hours, followed by exposition to air of the products obtained, or by dissolving into acids (for instance 96% H2SO4) and reprecipitation in iced H2O. This method is reported as an example in the case of Zn (II): In a 25 ml Erlenmeyer flask containing pyridine (10 ml) TTDPzH2 (224 mg; about 0,41 mmols) and hydrated zinc acetate (235 mg; 1.07 mmols) are introduced. The blue suspension is stirred at room temperature for 3 hours.

The solid is separated by centrifugation, washed with water and ethanol and eventually brought to constant weight under vacuum. A purple powder (233 mg; yield about 87%) is obtained. Both IR spectrum and thermogravimetric analysis suggest the formation of an hydrated product, TTDPzZn (H20) x (x = 2-4).

EXAMPLE 8 The complexes of class 4 are obtained by full desolvation of the species belonging to classes 1), 2) and 3), such desolvation being obtained by heat treatment under vacuum (classes 1) and 2)): 10-2 mmHg, 300 C°, 1 hour; class 3): 10-2 mmHg, 100 C°, 1 hour, or by sublimation under vacuum (10-2 mmHg) at a high temperature (400-500 C°).

EXAMPLE 9 The products of class 5) are obtained by a direct cyclotetramerization method from DCTD and anhydrous metal halogenide in a dry environment using a boiling heterocycle base (for example quinoline) as a reaction means.

ABBREVIATIONS DAMN, diaminomaleodinitryl DCSeD, 5-thiadiazole DCTD, 5-selenodiazole DMSO, dimethylsulphoxide Py, pyridine TSeDPzH2, tetra (selenediazolo) porphyrazine TTDPzH2, tetra (thiadiazolo) porphyrazine