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Title:
CHEMICAL FRAMEWORK COMPOSITIONS AND METHODS OF USE
Document Type and Number:
WIPO Patent Application WO/2009/149381
Kind Code:
A2
Abstract:
The disclosure provides metal organic frameworks useful for sensing, gas sorption, microelectronics and switches.

Inventors:
YAGHI, Omar, M. (435 Dalehurst Avenue, Los Angeles, CA, 90024, US)
LI, Qiaowei (10939 Palms Boulevard, Apt. 1Los Angeles, CA, 90034, US)
MILJANIC, Ognjen, S. (1126 N. Formosa Avenue, #3West Hollywood, CA, 90046, US)
STODDART, James, Fraser (2720 Noyes Street, Evanston, IL, 60201, US)
ZHANG, Wenyu (3270 Sawtelle Boulevard, #104Los Angeles, CA, 90066, US)
Application Number:
US2009/046463
Publication Date:
December 10, 2009
Filing Date:
June 05, 2009
Export Citation:
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Assignee:
THE REGENTS OF UNIVERSITY OF CALIFORNIA (1111 Franklin Street, 5th FloorOakland, CA, 94607, US)
YAGHI, Omar, M. (435 Dalehurst Avenue, Los Angeles, CA, 90024, US)
LI, Qiaowei (10939 Palms Boulevard, Apt. 1Los Angeles, CA, 90034, US)
MILJANIC, Ognjen, S. (1126 N. Formosa Avenue, #3West Hollywood, CA, 90046, US)
STODDART, James, Fraser (2720 Noyes Street, Evanston, IL, 60201, US)
ZHANG, Wenyu (3270 Sawtelle Boulevard, #104Los Angeles, CA, 90066, US)
International Classes:
C07F1/02; B01D53/00; C07D209/48; C07D325/00; C07D409/02; C07D409/04; H01H1/02
Domestic Patent References:
WO2004101575A22004-11-25
Other References:
SJ LOEB: 'Rotaxanes as ligands: from molecules to materials' CHEMICAL SOCIETY REVIEWS vol. 36, 2007, pages 226 - 235
LUCIA CARLUCCI ET AL.: 'Polycatenation, polythreading and polyknotting in coordination network chemistry' COORDINATION CHEMISTRY REVIEWS vol. 246, 2003, pages 247 - 289
SS HAN ET AL.: 'Improved designs of metal-organic frameworks for hydrogen storage' ANGEW. CHEM. INT. ED. vol. 46, 2007, pages 6289 - 6292
AG WONG-FOY ET AL.: 'Exceptional H2 saturation uptake in microporous metal- organic frameworks' J. AM. CHEM.SOC. vol. 128, 2006, pages 3794 - 3495
PETER R. ASHTON ET AL.: 'Hydrogen-Bonded Complexes of Aromatic Crown Ethers with (9-Anthracenyl)methylammonium Derivatives.' J. AM. CHEM. SOC. vol. 119, no. 44, 1997, pages 10641 - 10651
Attorney, Agent or Firm:
BAKER, Joseph, R. (Gavrilovich, Dodd & Lindsey LLP4660 La Jolla Village Drive, Suite 75, San Diego CA, 92122, US)
Download PDF:
Claims:

WHAT IS CLAIMED IS:

1. A metal organic framework comprising moieties with stereospecific and stereoelectronic control, pseudorotaxanes, rotaxanes, catenanes, chelates or cryptand structures.

2. The metal organic framework of claim 1, wherein a linking moiety connecting at least two monodentate of polydentate groups is chemically bonded to a macrocycle or a functional group with stereospecific and stereoelectronic control.

3. The metal organic framework of claim 2, wherein the macrocycle is selected from the group consisting of a crown ether; a cyclic macromolecule comprising C, O, N, S; and a macromolecular cyclic portion of any of the foregoing.

4. The metal organic framework of claim 2, wherein the macrocycle or functional group is selected from the group consisting of:

5. The metal organic framework of claim 1, wherein a linking moiety connecting at least two monodentate or polydentate groups comprises a structure selected from the group consisting of structures 1-XXX or any combination thereof.

6. The metal organic framework of claim 1 , wherein the organic framework is a cantenane framework.

7. The metal organic framework of claim 1 , wherein the cantenane framework comprises linking moieties having a structure selected from the group consisting of structures XXXI-XXXIII.

8. An organic framework comprising a plurality of pores and a stereospecific and stereoelectronic selective group bonded to a linking moiety, wherein the stereospecific and stereoelectronic selective group comprises a macrocycle or functional group thereof extending into at least one of the plurality of pores.

9. The organic framework of claim 8, comprising the general structure M-L-M, wherein M comprises a monodentate or polydentate group and L comprise a linking moiety.

10. The reticulated organic framework of claim 8, wherein the linking moiety is bonded to a macrocycle or functional group selected from the group consisting of:

1 1. The organic framework of claim 8, wherein the linking moiety comprises a structure selected from the group consisting of structure 1-XXXII and XXXIII.

12. The organic framework of claim 1 1, wherein the linking moieties are homogenous in the organic framework.

13. The organic framework of claim 1 1 , wherein the linking moieties are heterogeneous in the organic framework.

14. The framework of any of claim 2-13, wherein the linking moiety comprises a carboxylic functional group.

15. The framework of any of claims 2-13, wherein the monodentate or polydentate group comprises a metal.

16. The framework of claim 15, wherein the metal is a transition metal.

17. The framework of any of claims 2-13, wherein the monodentate or polydentate group comprises a metal selected from the group consisting Of Li + , Na + , Rb + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Ti 4+ , Zr 4+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Au + , Zn 2+ , Al 3+ , Ga 3+ , In 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Bi 5+ , Bi 3+ , and combinations thereof.

18. A microelectronic switch comprising a metal organic framework of any of claims 1-13.

19. The microelectronic switch of claim 18, wherein at least two monodentate or multidentate cores are linked to one another by a structure selected from the group consisting of structures I-XXXIII and any combination thereof.

20. A sensor comprising a framework of any one of claims 1-13.

21. A gas separation device comprising a framework of any one of claims 1-13.

22. A small molecule separation/purification device comprising a framework of any one of claims 1-13.

23. A guest recognition device comprising a framework of any one of claims 1-13.

24. A chiral molecule separation medium comprising a framework of any one of claims 1-13.

Description:

CHEMICAL FRAMEWORK COMPOSITIONS AND METHODS OF

USE

STATEMENT AS TO FEDERALLY SPONSORED RESEARCH [ 0001 ] This invention was made with Government support of Grant No. W91 INF-

06- 1 -0405, awarded by the Department of the Army and Grant No. H94003-06-2-0607, awarded by the Department of Defense. The Government has certain rights in this invention.

CROSS REFERENCE TO RELATED APPLICATIONS

[ 0002 ] This application claims priority under 35 U. S. C. § 1 19 from Provisional

Application Serial No. 61/059,224, filed June 5, 2008, the disclosure of which is incorporated herein by reference. .

TECHNICAL FIELD

[0003] The disclosure provides metal organic frameworks useful for sensing, gas sorption and separation, guest recognition, microelectronics and switches.

BACKGROUND

[0004] Molecular architecture is important for developing various materials both biologic and non-biologic. Biological systems use many 'architectural domains' to carry out specific tasks leading to complex functions. This concept is useful because such domains operate independently, yet they are connected.

SUMMARY

[0005] The disclosure provides a new class of organic frameworks based upon metal organic frameworks (MOFs). The new class goes beyond open reticulated geometries and are referred to herein as BORG frameworks, a new class of porous metal-organic materials. The BORG frameworks of the disclosure comprise one or more active domains that provide selective interactions with guest molecules useful for recognition and switching.

[0006] The disclosure provides a core structure comprising a MOF, wherein the struts linking monodentate or polydentate groups are modified with stereoelectronic selective groups. For example, in certain embodiments, MOFs comprising modified struts having molecule selective groups can be generated from electron donor links that recognize molecules that are electron acceptors. Furthermore, BORGs are frameworks in which

active domains are placed in a regular three-dimensional array, and these domains are addressable to incoming substrates or stimuli (including chemical, electrochemical or photophysical).

[0007] The disclosure provides the design and synthesis of porous crystals composed of several architectural domains that are useful for the docking of molecules in a manner akin to the well-known molecular docking of drug molecules.within protein targets. [ 0008] The disclosure provides a metal organic framework comprising moieties with stereospecific and stereoelectronic control, pseudorotaxanes, rotaxanes, catenanes, chelates or cryptand structures. In one embodiment, the framework comprises a linking moiety connecting at least two monodentate of polydentate groups wherein the linking moiety is chemically bonded to a macrocycle or a functional group with stereospecific and stereoelectronic control. In yet another embodiment, the macrocycle is selected from the group consisting of a crown ether; a cyclic macromolecule comprising C, O, N, S; and a macromolecular cyclic portion/functional group with stereospecific and stereoelectronic control of any of the foregoing. In another embodiment, a linking moiety connecting at least two monodentate or polydentate groups comprises a structure selected from the group consisting of structures I-XXX or any combination thereof. In yet another embodiment, the organic framework is a cantenane framework. In yet a further embodiment, the cantenane framework comprises linking moieties having a structure selected from the group consisting of structures XXXI-XXXl II.

[0009] The disclosure also provide an organic framework comprising a plurality of pores and a stereospecific and stereoelectronic selective group bonded to a linking moiety, wherein the stereospecific and stereoelectronic selective group comprises a macrocycle or functional group thereof extending into at least one of the plurality of pores. In one embodiment, the framework comprises a general structure M-L-M, wherein M comprises a monodentate or polydentate group and L comprise a linking moiety, wherein the linking moiety is bonded to a macrocycle or functional group. In yet a further embodiment, the macrocycle or functional group is selected from the group consisting of:

In one embodiment, the linking moiety comprises a structure selected from the group consisting of structure I-XXXII and XXXIII. The linking moieties can be homogenous or heterogenous. In another embodiment, the monodentate or polydentate group comprises a metal such as a transition metal or a metal selected from the group consisting Of Li + , Na + , Rb + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Ti 4+ , Zr 4+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Au + , Zn 2+ , Al 3+ , Ga 3+ , In 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Bi 5+ , Bi 3+ , and combinations thereof. [0010] The disclosure also provides a microelectronic switch comprising a metal organic framework comprising a macrocycle or functional stereoselective and stereoelectronic portion thereof. In yet another embodiment, at least two monodentate or multidentate cores are linked to one another by a structure selected from the group consisting of structures I-XXXIII and any combination thereof.

[0011] The disclosure also provides sensors, gas separation devices, small molecule separation/purification devices, guest recognition devices an chiral separation medium comprising any of the organic frameworks and BORGs described herein.

[0012] In yet another embodiment, a framework of the disclosure comprises a crystal structure or refined structure as set forth in Tables 6-10.

[0013] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.

DESCRIPTION OF DRAWINGS

[0014] Fig. 1. Schematic illustration of sorting domain, coverage domain and active domain in porous frameworks.

[0015] Fig. 2. Ball-and-stick drawings of crystal structures of MOF-1000, BORG¬

IA, BORG-I , BORG-2, and their corresponding organic struts. MOF-1000 (A) is a fourfold interpenetrating structure with different nets shown in four different colors. Single X- ray crystallography revealed BORG-IA (B) as a triply interpenetrating cubic structure (shown in blue, gold and gray), with polyethers represented by red balls and wires. BORG-I (C) and BORG-2 (D) share the identical cubic framework backbone, and different crown ethers are placed precisely throughout the whole network (Zn4θ(COO)6 polyhedra, blue; organic struts, gray; crown ethers, red). Crown ethers in all the structures were modeled by Cerius 2 . All hydrogen atoms have been omitted for clarity.

[0016] Fig. 3. Space filling illustration of MOF-1000 (A), BORG-IA (B), BORG-I

(C), and BORG-2 (D). The same color codes with Fig. 2 were applied. [0017] Fig. 4. X-ray diffraction and solid-state NMR spectroscopic studies on

BORG-I, BORG-I pseudorotaxanes, and their analogous molecular struts. Optical images of uncomplexed BORG-I crystals (A) and complexed BORG-I crystals (C) under the same optical view showed the single-crystal-to-single-crystal transformation. The resulting BORG-I pseudorotaxanes remain the original high crystallinity, which was confirmed by X-ray diffraction (B). Structures of BORG-I (D) and BORG-I pseudorotaxanes (F) are illustrated in ball-and-stick models. Docking Of PQT 2+ in BORG-I resulted in the upfield shifts of 15 N CP/MAS signals (E). The same upfield shift trend was also found in the 15 N CP/MAS spectroscopic studies (H) on the PQT 2+ inclusion in strut 2 (G). The spectrum of free PQT 2+ had a 15 N signal centered at 207.0 ppm, while that of the [PQTc2] 2PF 6 (I) showed a mean shift of 202.1 ppm. Color schemes: Zn 4 O(COO)6 polyhedra, gold; organic

strut, gray; BPP34C10, red; PQT 2+ , blue. All hydrogen atoms and counter ions have been omitted for clarity.

[0018] Fig. 5. Shows a scheme for the synthesis of intermediate Sl .

[ 0019] Fig. 6. Shows a scheme for the synthesis of intermediate Sl .

[0020] Fig. 7. Shows a scheme for the synthesis of S2.

[0021] Fig. 8. Shows a scheme for the synthesis of S3.

[0022] Fig. 9. Shows a step in the synthesis of strut 2 comprising a macrocycle.

[0023] Fig. 10. Shows a scheme for the synthesis of a strut useful in a BORG of the disclosure.

[0024] Fig. 11. Shows a scheme for the synthesis of struts 2 of a BORG of the disclosure.

[0025] Fig. 12. Shows a scheme for the synthesis of macromolecule S8.

[0026] Fig. 13. Shows a scheme for the synthesis of a strut linked to S8.

[ 0027] Fig. 14. Shows a scheme for the synthesis of BPP34C10DME useful as a strut in a BORG of the disclosure.

[0028] Fig. 15. Shows a scheme for the synthesis of structure Sl 1.

[0029] Fig. 16. Shows a scheme for the synthesis of strut 3 useful in a BORG framework of the disclosure.

[ 0030] Fig. 17. Shows a scheme for the synthesis of l5 N-labeIed PQT-2PF 6 .

[0031] Fig. 18. UV / vis (dashed lines) and emission (solid lines) spectra of strut 2

(20.0 μM, orange) and the pseudorotaxane [PQTc2]-2PFό (20.0 μM, orange) in Me2CO at room temperature, absorption λmax = 377 nm. Insert: UV / vis spectra of strut 2 (0.500 mM, orange) and the pseudorotaxane [PQTc2] '2PFo(O-SOO mM, orange). The charge-transfer absorption (λ

= 430 - 450 nm) of [PQTc2]-2PFό overlaps with the emission (λ = 458 nm) of strut 2. The fluorescence is thus quenched upon formation of the pseudorotaxane.

[0032] Fig. 19. AA vs. [PQT]/. The concentration of strut 2 was kept constant at 0.500 mM. Optical pathway = 1.0 cm. The continuous line was calculated for K = 829 ± 71 M-i and

δs = 944 ± 19 VT 1 1 Cm "1 .

[0033] Fig. 20. Shows the formation of the pseudorotaxane [PQTc2]-2PF 5 .

[0034] Fig. 21. Shows 1 H NMR spectra of PQT-2PFa ( 1.2 x 10 ~3 mM) : 2 (4.0 x 1(T* mM) = 3 : 1 in CD3COCD3 at various temperatures. The exchange of the complexed and uncomplexed PQT 2+ was slowed down at lowered temperatures, causing the separation of signals for α, β, and N-Me protons from the PQT 2+ .

[0035] Fig. 22. Shows 1 H- 1 H COSY NMR spectrum and 1 H- 13 C HMQC spectrum of PQT-2PF6 (1.2 x 10 "3 mM) : 2 (4.0 x 10^ mM) = 3 : 1 in CD3COCD3 at 200 K.

Correlations among nuclei from PQT, (4-carboxyphenyl)ethynyl, and hydroquinone moieties are indicated.

[0036] Fig. 23. Shows 15 N NMR Spectra of a) PQT-2PF6 (1.2 x 10 ~3 mM) and b)

PQT 2PF6 (1.2 x 10 ~3 mM) : 2 (4.0 x lO^ mM) = 3 : 1 in CD3COCD3 at 200 K.

Complexed PQT2+ (205.2 ppm) displayed a chemical shift 1.7 ppm lower than the uncomplexed species (206.9 ppm) as the consequence of the shielding effect of the crown ether.

[0037] Fig. 24. Shows comparison of solid-state 13C CP/MAS NMR spectra of

BORG-I pseudorotaxanes (top), BORG-I (middle), and PQT 2PF6 (bottom). The 13C

CP/MAS NMR spectrum of BORG-I pseudorotaxanes did not show a significant shift compared to those of BORG-I and free PQT 2PF6.

[0038] Fig. 25. Shows solid-state 15N CP/MAS NMR spectra of [PQTc2] 2PF 6 .

Mole ratios of PQT 2PF6 with strut 2 are 1 :2.0 (top), 1 :1.0 (2 nd from top), 2.0: 1 (middle), and 4.0: 1 (2 nd from bottom). The 15N CP/MAS NMR spectrum of pure PQT 2PF6 is shown in red. The mean chemical shift of 15N in free PQT 2PF6 was 207.0 ppm, while that of the complexed PQT 2PF6 was 202.1 ppm.

[0039] Fig. 26. Shows solid-state 15N CP/MAS NMR spectra of BORG-I pseudorotaxanes. Mole ratios of PQT 2PF6 with BPP34C10 in BORG-I were 1 : 1.8, 1 :1 ,

1.8: 1, 2.5: 1. The mean chemical shift of 15N in free PQT-2PF6 was 207.2 ppm, while that in PQT 2PF6 complexed with BORG-I was 204.6 ppm.

[0040] Fig. 27. Shows solid-state 15N CP/MAS NMR spectra of BORG-I pseudorotaxanes (BORG-I and PQT 2PF6 in 1 : 1 ratio) at variable temperature from 173 to

373 K. No peak split or widening was observed.

[0041] Fig. 28. Shows IH NMR spectrum of BORG-I pseudorotaxanes after digestion. Integrations of peaks at 7.96 ppm (d, 4H, Ar-H a in 2, 3 J = 8.5 Hz) and 4.60 ppm

(s, 6H, N-CH 3 in PQT 2+ ) in 1 H show that the ratio Of PQT 2+ to strut 2 is 1 : 1.

[0042 ] Fig. 29. Shows 1 H NMR spectrum Of PQT 2+ included MOF-177 after digestion. Integrations of peaks at 8.08 ppm ( 15 H, Ar-H in H3BTB) and 4.53 ppm (s, 6H, N-

CH 3 in PQT 2+ ) in 1 H show that less than 0.06 PQT 2+ was included for each BTB strut.

10043 ] Fig. 30. Shows an ORTEP drawing of the asymmetric unit of [PQTc:2] 2PF 6 .

Hydrogen atoms, solvent molecules and anions were excluded for clarity. Only one component of each disordered group is shown.

[0044] Fig. 31. Shows an ORTEP drawing of the asymmetric unit of MOF-1000, excluding hydrogen atoms and solvents.

[0045] Fig. 32. Shows an ORTEP drawing of BORG-IA, with a full Zn 4 O SBU and

1.5 links. Hydrogen atoms, hydroquinone rings and partial bismethylenedioxy units of the tetraethylene glycol loops in BPP34C10 are not shown.

[0046] Fig. 33. Shows an ORTEP drawing of BORG- 1 asymmetric unit with both components of disorder shown, excluding the crown ethers, hydrogen atoms and guest entities. All ellipsoids are displayed at the 10% probability level.

[0047] Fig. 34. Shows an ORTEP drawing of BORG-I framework with only one component of the disorder shown, excluding the crown ethers, hydrogen atoms and guest entities. All ellipsoids are displayed at the 10% probability level. [0048] Fig. 35. Shows a comparison of the experimental PXRD pattern of as- synthesized MOF-1000 (top) with the one simulated from its single crystal structure (bottom). The very high degree of correspondence between the patterns indicates that the bulk material has the same structure as the single crystal.

[0049] Fig. 36. Shows a comparison of the experimental PXRD pattern of as- synthesized BORG-I (top) with the one simulated from its single crystal structure (bottom). The very high degree of correspondence between the patterns indicates that the bulk material has the same structure as the single crystal.

[0050] Fig. 37. Shows a comparison of the experimental PXRD pattern of as-prepared

BORG-2 (top) with the one simulated from its single crystal structure (bottom, identical with BORG-I simulation). The very high degree of correspondence between the patterns indicates that the bulk material has the same structure as the single crystal.

[ 0051 ] Fig. 38. Shows a comparison of the experimental PXRD patterns of BORG-I pseudorotaxanes (top) and BORG-I (as-synthesized, middle; simulated, bottom). The framework retains the same structure after inclusion of paraquat. [0052 ] Fig. 39. Shows an overlay of TGA traces of MOF-1000. As-synthesizee, chloroform (pentene stabilized) exchanged, framework only.

[0053] Fig. 40. Shows the overlay of TGA traces of BORG-I . As-synthesized,

Me 2 CO exchanged, framework only.

[0054] Fig. 41. Shows The overlay of TGA traces of BORG-2. As-synthesized,

Me 2 CO exchanged, framework only.

[0055] Fig. 42. Shows a TGA trace of BORG-I pseudorotaxanes framework. The material is thermally stable to 300 0 C. Before the TGA experiment, the sample was evacuated at room temperature for 12 h after removing the sample from a saturated solution of paraquat in

Me 2 CO.

DETAILED DESCRIPTION

[0056] As used herein and in the appended claims, the singular forms "a," "and," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a species" includes a plurality of such species and reference to "the framework" includes reference to one or more frameworks and equivalents thereof, and so forth.

[0057] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. Although any methods and reagents similar or equivalent to those described herein can be used in the practice of the disclosed methods and compositions, the exemplary methods and materials are now described.

[0058] Also, the use of "or" means "and/or" unless stated otherwise. Similarly,

"comprise," "comprises," "comprising" "include," "includes," and "including" are interchangeable and not intended to be limiting.

[0059] It is to be further understood that where descriptions of various embodiments use the term "comprising," those skilled in the art would understand that in some specific instances, an embodiment can be alternatively described using language "consisting essentially of or "consisting of."

[0060] All publications mentioned herein are incorporated herein by reference in full for the purpose of describing and disclosing the methodologies, which are described in the publications, which might be used in connection with the description herein. The publications discussed above and throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior disclosure.

[0061] Metal-organic frameworks (MOFs) are a class of crystalline porous materials whose structure is composed of metal-oxide units joined by organic linkers through strong covalent bonds. The flexibility with which these components can be varied has led to an

extensive class of MOF structures with ultra-high surface areas, far exceeding those achieved for porous carbons. MOFs exhibit high thermal stability, with decomposition between 350 0 C and 400 0 C in the case of MOF-5 (Eddaoudi M, et ai, Science 295:469- 472, 2002), ensuring their applicability across a wide temperature range. The unprecedented surface area and the control with which their pore metrics and functionality can be designed provides limitless potential for their structure to be tailored to carry out a specific application, thus suggesting the possibility of being superior to activated carbons in many applications.

[0062 ] The vast majority of porous MOFs prepared thus far can be regarded as having two important architectural domains: the pore aperture which is responsible for the shape- and size-selective binding of incoming molecules (sorting domain) and the internal surface of the pores onto which gases such as hydrogen and methane can be compacted and randomly distributed next to each other by virtue of their weak interactions with adsorption sites covering the struts and joints (coverage domain) (see, e.g., Figure 1). The synthesis of more complex MOFs, however, where more than two domains are present, remains unexplored.

[0063] The disclosure shows the integration of stereoelectronic selective moieties in a modular fashion into struts of MOFs, thereby creating recognition sites into which incoming guests will dock in a highly specific manner with stereoelectronic control (active domain). The distinction between these three different domains (sorting, coverage, and selective) is depicted in Figure 1. The disclosure thus provides frameworks in which a third functional domain is added to organic frameworks that combines shape, size and electronic elements in the recognition of incoming guests, and brings order to otherwise highly disordered guests in conventional MOFs. Accordingly, the disclosure provides new MOFs that are beyond open reticulated geometries (BORGs).

[ 0064] The BORGs of the disclosure are based upon an underlying metal organic frameworks having the general structure M-L-M, wherein L is a linking moiety or "strut" and M is a monodentate or multidentate linking cluster (e.g., a transition metal) and wherein L is functionalized to comprise a stereoelectronic selective group having, in one embodiment, an electron donor or acceptor capacity. In another embodiment, the underlying MOF linking moiety or strut comprises a carboxylic acid functional group that can be used in bond formation with a macrocycle. The functional group is used to bond/conjugate a stereoelectronic selective group to impart selectivity in a pore of a framework.

[0065] The BORGs presented here combine the precise positioning of the active domains with docking as an expression of molecular recognition. This property can be exemplified through the molecular recognition behavior of the macrocyclic polyethers (structures 2 and 3) as docking sites. For example, when BORG-I crystals were introduced into a saturated solution of PQT»2PF 6 in Me 2 CO, the crystals immediately turned red (Fig. 4, A and C) — a typical behavior for this binding event that indicates significant charge- transfer interactions between the PQT 2+ dications and crown ether rings. This observation points to the formation of BORG-I pseudorotaxanes by threading of the PQT 2+ dication through the middle of the crown ether. The reversibility of such process was evidenced by the reappearance of the original light yellow color upon rinsing with Me 2 CO. Furthermore, the complexed BORG-I maintained the original high crystallinity of the parent framework, as confirmed by their coincident powder X-ray diffraction (PXRD) patterns (Fig. 4B). The BORG constructs represent a significant advance towards bringing order in three- dimensions to the otherwise random placement of active molecules either on surfaces or at interfaces.

[0066] As used herein, a "core" refers to a repeating unit or units found in a framework. Such a framework can comprise a homogenous repeating core or a heterogeneous repeating core structure. A core comprises a monodentate or multidentate group (e.g., a transition metal or cluster of transition metals) and a linking moiety. A plurality of cores linked together defines a framework.

[0067] The term "cluster" refers to identifiable associations of 2 or more atoms.

Such associations are typically established by some type of bond-ionic, covalent, Van der Waals, and the like.

[0068] A "linking cluster" refers to one or more reactive species capable of condensation comprising an atom capable of forming a bond between a linking moiety and a metal group or between a linking moiety and another linking moiety or between a linking moiety and a molecule selective group. In some embodiments, the linking cluster may comprise one or more different reactive species capable of forming a link with, for example, a bridging oxygen atom. For example, a linking cluster can comprise CO 2 H, CS 2 H, NO 2 , SO 3 H, Si(OH) 3 , Ge(OH) 3 , Sn(OH) 3 , Si(SH) 4 , Ge(SH) 4 , Sn(SH) 4 , PO 3 H, AsO 3 H, AsO 4 H, P(SH) 3 , As(SH) 3 , CH(RSH) 2 , C(RSH) 3 , CH(RNH 2 ) 2 , C(RNH 2 ) 3 , CH(ROH) 2 , C(ROH) 3 , CH(RCN) 2 , C(RCN) 3 , CH(SH) 2 , C(SH) 3 , CH(NH 2 ) 2 , C(NH 2 ) 3 , CH(OH) 2 , C(OH) 3 ,

CH(CN) 2 , and C(CN) 3 , wherein R is an alkyl group having from 1 to 5 carbon atoms, or an aryl group comprising 1 to 2 phenyl rings.

[0069] Generally a linking moiety comprises a substructure covalently linked to an alkyl or cycloalkyl group, comprising 1 to 20 carbon atoms, an aryl group comprising 1 to 5 phenyl rings, or an alkyl or aryl amine comprising alkyl or cycloalkyl groups having from 1 to 20 carbon atoms or aryl groups comprising 1 to 5 phenyl rings, and in which a linking cluster (e.g., a multidentate function groups) can become covalently bound to the substructure. A cycloalkyl or aryl substructure may comprise 1 to 5 rings that comprise either of all carbon or a mixture of carbon with nitrogen, oxygen, sulfur, boron, phosphorus, silicon and/or aluminum atoms making up the ring. Typically the linking moiety will comprise a substructure having one or more carboxylic acid linking clusters covalently attached.

[0070] As used herein, a line in a chemical formula with an atom on one end and nothing on the other end means that the formula refers to a chemical fragment that is bonded to another entity on the end without an atom attached. Sometimes for emphasis, a wavy line will intersect the line.

[0071 ] Transition metals useful in the formation of a BORG comprise any one or more of the following: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh,

Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, and

Uub. In a specific embodiment, the transition metal is Zn or Co.

[0072 ] A BORG can comprise a MOF substructure wherein the framework comprises a plurality of metal clusters comprising a metal ion and a linking moiety having a general structure selected from the group consisting of:

wherein M is a metal and wherein a benzene ring of the linking ligand is bonded to a macrocycle such as, for example, a crown ether.

[0073] It will be recognized that the linking moieties or struts of the disclosure can comprise any number of known linking moieties for existing MOFs. Furthermore, one of skill with recognize that that linking moieties may be generalized or derivatized so long as they comprise a functional group capable of bonding to a macrocycle or stereoelectonic selective group and a linking cluster that can bind to a monodentate or mutidentate cluster. For example, a linking moiety may comprise:

wherein each of Rl-15 are independently selected from the group consisting of -H, -OH, - OR 16 , aryl, substituted aryl, alkyl, substituted alkyl, carboxyl, aminocarbonyl, alkylsulfonylaminocarboxyl, alkoxycarbonyl, and halo, wherein R 16 can be -H, and aryl, substituted aryl, alkyl, substituted alkyl, carboxyl, aminocarbonyl, alkylsulfonylaminocarboxyl, alkoxycarbonyl, and halo.

[0074] The term "alkyl" refers to a saturated monovalent chain of carbon atoms, which may be optionally branched; the term "cycloalkyl" refers to a monovalent chain of carbon atoms, a portion of which forms a ring; the term "alkenyl" refers to an unsaturated monovalent chain of carbon atoms including at least one double bond, which may be optionally branched; the term "cycloalkenyl" refers to an unsaturated monovalent chain of carbon atoms, a portion of which forms a ring; the term "heterocyclyl" refers to a monovalent chain of carbon and heteroatoms, wherein the heteroatoms are selected from nitrogen, oxygen, and sulfur, a portion of which, including at least one heteroatom, form a ring; the term "aryl" refers to an aromatic mono or polycyclic ring of carbon atoms, such as phenyl, naphthyl, and the like; and the term "heteroaryl" refers to an aromatic mono or polycyclic ring of carbon atoms and at least one heteroatom selected from nitrogen, oxygen, and sulfur, such as pyridinyl, pyrimidinyl, indolyl, benzoxazolyl, and the like. It is to be understood that each of alkyl, cycloalkyl, alkenyl, cycloalkenyl, and heterocyclyl may be optionally substituted with independently selected groups such as alkyl, haloalkyl, hydroxyalkyl, aminoalkyl, carboxylic acid and derivatives thereof, including esters, amides,

and nitrites, hydroxy, alkoxy, acyloxy, amino, alkyl and dialkylamino, acylamino, thio, and the like, and combinations thereof. It is further to be understood that each of aryl and heteroaryl may be optionally substituted with one or more independently selected substituents, such as halo, hydroxy, amino, alkyl or dialkylamino, alkoxy, alkylsulfonyl, cyano, nitro, and the like.

[0075] A framework (e.g., a BORG) of the disclosure can take any framework/structure. For example, using the methods of the disclosure, BORGs having any of the following framework codes can be obtained: ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AWO, AWW, BCT, BEA, BEC, BIK, BOG, BPH, BRE, CAN, CAS, CDO, CFI, CGF, CGS, CHA, CHI, CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EON, EPI, ERI, ESV, ETR, EUO, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFR, IHW, ISV, ITE, ITH, ITW, IWR, IWV, IWW, JBW, KFI, LAU, LEV, LIO, LIT, LOS, LOV, LTA, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ, MSE, MSO, MTF, MTN, MTT, MTW, MWW, NAB, NAT, NES, NON, NPO, NSI, OBW, OFF, OSI, OSO, OWE, PAR, PAU, PHI 1 1 PON, POZ, RHO, RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAO, SAS, SAT, SAV, SBE, SBS, SBT, SFE, SFF, SFG, SFH, SFN, SFO, SGT, SIV, SOD, SOS, SSY, STF, STI, STT, SZR, TER, THO, TON, TSC, TUN, UEI, UFI, UOZ, USI, UTL, VET, VFI, VNI, VSV, WEI, WEN, YUG, and ZON.

[0076] Various molecule selective groups (e.g., stereoelectronic groups) can be used to modify the strut or linking moiety of an underlying MOF structure to generate a BORG. In one embodiment, various macrocycles can be conjugated or bonded to the MOF strut to generate a BORG. Numerous macrocycles are known in the art. A macrocycle is, as defined by IUPAC, "a cyclic macromolecule or a macromolecular cyclic portion of a molecule." In the chemical literature, organic chemists may consider any molecule containing a ring of seven or more atoms to be a macrocyle. For example, modifications to the underlying strut in a MOF with a macrocycle can generate pseudorotaxanes, rotaxanes, catenane, chelates and cryptands structures. Such modified frameworks are useful in various compositions and systems including, but not limited to, gas separation and purification, sensors, and microelectronic switches.

[0077] A rotaxane is a mechanically-interlocked molecular architecture consisting of a "dumbbell shaped molecule" which is threaded through a "macrocycle". The two

components of a rotaxane are kinetically trapped since the ends of the dumbbell (often called stoppers) are larger than the internal diameter of the ring and prevent disassociation (unthreading) of the components since this would require significant distortion of the covalent bonds. Examples of rotaxane have been found in biological systems including: cystine knot peptides, cyclotides or lasso-peptides such as microcin J25 are protein, and a variety of peptides with rotaxane substructure.

[0078] Other mechanically-interlocked molecular architectures, such as catenanes, can also be generated and are provided by the disclosure. A catenane is a mechanically- interlocked molecular architecture comprising two or more interlocked macrocycles. Typically the interlocked rings cannot be separated without breaking the covalent bonds of the macrocycles. As mentioned elsewhere herein, catenane structures are conceptually related to other mechanically-interlocked molecular architectures, such as rotaxanes, molecular knots or molecular Borromean rings.

[0079] Borromean rings are an example of a mechanically-interlocked molecular architecture in which three macrocycles are interlocked in such a way that breaking any macrocycle allows the others to disassociate.

[0080] The BORG frameworks comprising any of the foregoing general structural descriptions can be used for a multitude of purposes including, but not limited to, molecular electronics as logic molecular switching elements and as molecular shuttles. Controlling the position of the macrocycle allows the BORG to function as molecular switch with each possible location of the macrocycle corresponding to a different state. These BORG-based machines can be manipulated both by chemical and photochemical inputs. The BORG frameworks of the disclosure comprising, for example, pseudorotaxanes, rotaxanes, and catenane structures can be used in molecular purification, reactions, catalysts, molecular switches, electronic devices and molecular sensors.

[0081] The BORG frameworks of the disclosure can be designed to includes redox- active groups (e.g. viologen, TTF=tetrathiafulvalene), photoisomerizable groups (e.g. azobenzene), fluorescent groups and chiral groups.

[0082 ] Exemplary molecule selective groups can include, but are not limited to, ethers, crown ethers and their substituents and derivatives. Oxygen atoms in ethers or crown ethers can be replaced by S, CRi R2 or NRi, wherein Ri, R 2 can be H or any organic group; this includes, for example, derivatives of EDTA (Diaminoethanetetraacetic acid). In the exemplary list of macrocycles below, it will be recognized that the length of the chain/cycle

can be any length as will be recognized in the art. Furthermore, a BORG structure of the disclosure may comprise a homogenous or heterogeneous (Le , combination) of the structures below. The dashed arrows are positions for connectivity to the underlying strut of a MOF. Exemplary macrocycles that can be linked to a MOF strut include molecules (or combinations thereof) selected from the group consisting of:

[0083] For example, macrocycles above can be covalently linked to a strut of an underlying MOF to generate a BORG. Exemplary struts comprising a macrocycle or polyether that can be used in the generation of BORGs can be selected from the group below (including combinations thereof):

[0084 ] Exemplary BORG switches can comprise a strut with a macrocycle as set forth below:

[0085] Exemplary switchable BORGs comprising a macrocycle with at least two different moieties or catenanes include, but are not limited to, struts comprising the structures below:

[0086] A framework of the disclosure can be synthesized by using solvothermal methods. For example, BORG-I can be synthesized using metal ions having distinctly different coordination geometries, in combination with a linking moiety/strut possessing linking cluster function groups, and a suitable templating agent. [ 0087 ] Metal ions that can be used in the synthesis of BORGs of the disclosure include Li + , Na + , Rb + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Ti 4+ , Zr 4+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Au + , Zn 2+ , Al 3+ , Ga 3+ , In 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Bi 5+ , Bi 3+ , and combinations thereof, along with corresponding metal salt counter-anions.

[0088] The preparation of the BORGs of the disclosure can be carried out in either an aqueous or non-aqueous system. The solvent may be polar or non-polar as the case may be. The solvent can comprise the templating agent or the optional ligand containing a monodentate functional group. Examples of non-aqueous solvents include n-alkanes, such as pentane, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, cyanobenzene, aniline, naphthalene, naphthas, n-alcohols such as methanol, ethanol, n-propanol, isopropanol, acetone, 1 ,3, -dichloroethane, methylene chloride, chloroform, carbon tetrachloride, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, N- methylpyrollidone, dimethylacetamide, diethylformamide, thiophene, pyridine, ethanolamine, triethylamine, ethlenediamine, and the like. Those skilled in the art will be readily able to determine an appropriate solvent based on the starting reactants and the choice of solvent is not believed to be crucial in obtaining the materials of the disclosure. [0089] Templating agents can be used in the methods of the disclosure. Templating agents employed in the disclosure are added to the reaction mixture for the purpose of occupying the pores in the resulting crystalline base MOF structure or BORG. In some variations of the disclosure, space-filling agents, adsorbed chemical species and guest species increase the surface area of the metal-organic framework. Suitable space-filling agents include, for example, a component selected from the group consisting of: (i) alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms; (ii) aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings; (iii) alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms; (iv) aryl phosphonium salts, having from 1 to 5 phenyl rings; (v) alkyl

organic acids and their corresponding salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms; (vi) aryl organic acids and their corresponding salts, having from 1 to 5 phenyl rings; (vii) aliphatic alcohols, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms; or (viii) aryl alcohols having from 1 to 5 phenyl rings.

[0090] Crystallization can be carried out by leaving the solution at room temperature or in isothermal oven for up to 300 °C; adding a diluted base to the solution to initiate the crystallization; diffusing a diluted base into the solution to initiate the crystallization; and/or transferring the solution to a closed vessel and heating to a predetermined temperature. [0091] Typically, the precursor MOF or BORG is heated to a temperature from about 30 0 C to about 300 0 C. In another variation, the one or more templating agents are removed by exposing the precursor MOF or BORG to a vacuum. Typically, the vacuum is characterized by having a pressure less than 10 '3 torr. In other variations, from about 10 '5 torr to about 700 torr. In still another variation of the disclosure, the one or more ligands are removed by simultaneously heating the precursor MOF or BORG and by exposing the precursor MOF or BORG to a vacuum. In still another variation, the solution used in the method of the disclosure may also include space-filling agents. Examples of suitable spacefilling agents are set forth above. In a refinement of each of these variations, one or more ligands of the precursor MOF or BORG may be exchanged with another agent or agents that are more easily removed by subsequent heating and/or exposure to a vacuum. [0092 ] In another embodiment, the framework set forth above may include an interpenetrating framework that increases the surface area of the framework. Although the frameworks of the disclosure may advantageously exclude such interpenetration, there are circumstances when the inclusion of an interpenetrating framework may be used to increase the surface area. An exemplary interpenetrating framework includes MOF-1000 described herein.

[0093] The frameworks of the disclosure can be used as sorption devices. Sorption is a general term that refers to a process resulting in the association of atoms or molecules with a target material. Sorption includes both adsorption and absorption. Absorption refers to a process in which atoms or molecules move into the bulk of a porous material, such as the absorption of water by a sponge. Adsorption refers to a process in which atoms or molecules move from a bulk phase (that is, solid, liquid, or gas) onto a solid or liquid surface. The term adsorption may be used in the context of solid surfaces in contact with

liquids and gases. Molecules that have been adsorbed onto solid surfaces are referred to generically as adsorbates, and the surface to which they are adsorbed as the substrate or adsorbent. Adsorption is usually described through isotherms, that is, functions which connect the amount of adsorbate on the adsorbent, with its pressure (if gas) or concentration (if liquid). In general, desorption refers to the reverse of adsorption, and is a process in which molecules adsorbed on a surface are transferred back into a bulk phase. [0094] The metal-organic frameworks used in the embodiments of the disclosure include a plurality of pores for adsorption of a biological molecule or gas. In one variation, the plurality of pores has a unimodal size distribution. In another variation, the plurality of pores have a multimodal {e.g., bimodal) size distribution. In the case of a BORG the pore comprises a selective group capable of specifically binding a particular size, shape or charged entity. The BORG can be designed to be selective by incorporating a particular macrocycle or other stereoselective molecular entity into the underlying MOF. Such designing conjugates or links the stereoselective molecular entity to a strut of the underlying MOF, wherein the molecular entity extends into at least one pore of the MOF. [0095] Advantageously, the BORG framework includes one or more sites for binding or storing a biological molecule or gas. Thus the BORGs of the disclosure can serve as gas storage materials. Gases that may be stored in the gas storage material of the disclosure include gas molecules comprising available electron density for attachment to the one or more sites for storing gas. Suitable examples of such gases include, but are not limited to, the gases comprising a component selected from the group consisting of ammonia, argon, carbon dioxide, carbon monoxide, hydrogen, and combinations thereof. In one variation of this embodiment, the accessible metal site is an open metal site. [0096] Furthermore, the BORGs of the disclosure may be used as sensing materials.

For example, interaction of a BORG with a particular analyte can cause a change in the composition, electronics or optics of the BORG. Such changes can be detected using an appropriate transducing agent (e.g., a current flowing through the material to detect conductivity changes, an acoustic tranducer or balance to detect mass changes, or an optical detector to detect changes in color). An example of the sensing of such BORGs is illustrated by BORG-I upon absorption and desportion Of PQT 2+ .

[0097] The following examples are intended to illustrate but not limit the disclosure.

While they are typical of those that might be used, other procedures known to those skilled in the art may alternatively be used.

EXAMPLES

[0098 ] Chemicals were purchased from commercial suppliers and used as received, unless otherwise noted. Dry solvents were obtained from an EMD Chemicals DrySolv® system. Thin-layer chromatography (TLC) was carried out using glass plates, precoated with silica gel 60 with fluorescent indicator (Whatman LK6F). The plates were inspected by UV light (254 nm). Column chromatography was carried out using silica gel 6OF (230-400 mesh). 1 H, 13 C, and 15 N NMR spectra were recorded on ARX500 (500 MHz), DRX500 (500 MHz) or AV600 (600 MHz) spectrometers with the residual solvent as the internal standard. The chemical shifts were listed in ppm on the δ scale and coupling constants were recorded in Hertz (Hz). The following abbreviations were used to explain the multiplicities: s, singlet; d, doublet; t, triplet; q, quartet; b, broad peaks; m, multiplet or overlapping peaks. High- resolution electrospray ionization (ESI) mass spectra were measured on a Micromass Q-Tof Ultima (SCS, University of Illinois).

[0099] As a demonstration of the BORG frameworks of the disclosure, three long organic struts (19.3 A) incorporating 34- and 36-membered macrocyclic polyethers as recognition modules were used in the construction of several crystalline primitive cubic frameworks. BORG-I, for example, is capable of docking paraquat dications (PQT 2+ ) into each of the macrocyclic polyethers units located within its struts in a highly specific and stereoelectronically controlled fashion. This act of specific complexation yields the corresponding BORG-I pseudorotaxanes, as confirmed by X-ray diffraction and solid- state/solution NMR spectroscopic studies performed on BORG-I, its pseudorotaxanes, and their molecular strut analogues. A control experiment involving the attempted inclusion of PQT 2+ inside a framework (MOF- 177) devoid of polyether struts showed negligible uptake Of PQT 2+ dications, indicating the macrocyclic polyether docking Of PQT 2+ . Fundamentally, BORG constructs place active units (e.g., macrocyclic polyether docking sites) in a regular three-dimensional array, making them fully addressable in a selective, cohesive, and reproducible manner.

[00100] Primitive cubic topology of the archetypical MOF-5 was used, in which benzene struts are joined by Zn 4 O(CO 2 )O cluster joints. Initially, the feasibility of using the long 1/4DMBDA to make MOF-1000, which has the MOF-5 topology, albeit quadruply interpenetrated was demonstrated (Fig. 2A). This approach was extended to the more complex struts, BPP34C10DA and 1/5DNPPP36C10DA, which are known to act as electron-rich receptors for electron-deficient substrates, to make the corresponding BORG-

IA, BORG-I and BORG-2 (Fig. 2, B to D). Indeed each of the crown ether receptors in BORG-I is addressable as evidenced by the docking of the paraquat dication (PQT 2+ ) at every one of the receptor sites. In contrast to known MOFs where the frameworks are used mainly as passive platforms for the adsorption of gases and molecules, BORG-I not only has active components in precise recognition sites but also, by virtue of the openness of its structure, allows substrates to diffuse freely from solution, through the pores, and finally dock at these active domains.

[00101] Strut synthesis. Strut 1 (Sl) was synthesized by the attachment of 4- (carboxyphenyl)ethynyl groups to the 2- and 5-positions of a central 1 ,4-dimethoxybenzene ring using the Pd-catalyzed alkyne-aromatic Sonogashira coupling (see Fig. 5 and 6). Methyl 4-iodobenzoate (10.5 g, 40 mmol), Pd(PPh 3 ) 4 (0.46 g. 0.4 mmol), and CuI (0.16 g, 0.8 mmol) were added to a mixture of JPr 2 NH (15 mL) and DMF (100 mL). The mixture was purged with Ar while stirring for 30 min before a solution of 1 ,4-diethynyl-2,5- dimethoxybenzene (3.70 g, 20 mmol) (1) in DMF (40 mL) was slowly added. The mixture was stirred for 8 h at 80 0 C. After cooling to room temperature, the insoluble material was collected by filtration, and then washed with H 2 O (350 mL) and MeOH (100 mL). The yellow solid was dissolved in CHCb (1200 mL) and washed with H 2 O (300 mL) and dried (MgSO 4 ). The solvent was removed in vacuo to afford the product S3 (8.38 g, 92%) which was employed in the next step without further purification. 1 H NMR (500 MHz, CDCI3): δ = 8.02 (d, 4H, Ar-H a , 3 J = 8.4 Hz), 7.62 (d, 4H, Ar-H b , 3 J = 8.4 Hz), 7.04 (s, 2H, Ar-HQ), 3.93 (s, 6H, COOCH 3 ), 3.91 (s, 6H, OCH 3 ). ' 3 C NMR (125 MHz, CDC13): δ =166.4, 153.9, 131.5, 129.5, 129.4, 127.7, 115.5, 1 13.2, 94.3, 88.4, 56.4, 52.1. HiRes MS (ESI-TOF): Calcd. for [M + H] + C 28 H 23 O 6 + m/z = 455.1489; found m/z = 455.1492. Sl (1.00 g, 2.20 mmol) and NaOH (0.35 g, 8.80 mmol) were dissolved in a mixture of THF (50 mL) and H2O (50 mL). The solution was stirred at room temperature overnight. The pH of the solution was then adjusted to 2 with aqueous HCI solution (1 M) while a precipitate formed. The precipitate was collected by filtration, washed with H 2 O, and dried in air to afford the product 1 (0.920 g, 98%). 1 H NMR (500 MHz, CD3SOCD3): δ = 13.18 (s, 2H, COOH), 7.98 (d, 4H, Ar-H a , 3 J = 8.5 Hz), 7.66 (d, 4H, Ar-H b , 3 J = 8.5Hz), 7.25 (s, 2H, Ar-HQ), 3.87 (s, 6H, OCH3). 13 C NMR (125 MHz, CD3SOCD3) δ = 167.9, 154.0, 131.8, 131.0, 129.9, 127.0, 1 16.0, 1 12.8, 94.4, 89.0, 56.7. HiRes MS (ESI-TOF): Calcd. for [M + H] + C 26 H 19 O 6 + m/z = 427.1 176; found m/z = 427.1176.

[00102] S2: Ethyl 4-bromobenzoate (2.00 g, 8.73 mmol) was dissolved in DMF (80 mL) and iPr 2 NH (20 mL). Under Ar protection, TMS acetylene (1.29 g, 13.1 mmol), Pd(PPh 3 ) 4 (0.504 g, 0.437 mmol), and CuI (0.0430 g, 0.437 mmol) were added to the solution. The mixture was then stirred under Ar at 80 0 C for 48 h. The solvent was then removed in vacuo. The residue was then dissolved in CH 2 Cl 2 (50 mL) before being washed with H 2 O (20 mL x 2) and brine (20 mL). The organic phase was then dried (Na 2 SO 4 ). The solvent was removed in vacuo. Column chromatography (SiO 2 : Hexanes / CH2C12 = 3:1 ) provided the product S2 as a yellow solid (2.03 g, 94%). I H NMR (500 MHz, CDC13): δ = 7.77 (d, 2H, Ar-H a , 3 J = 8.7 Hz), 7.51 (d, 2H, Ar-H b , 3 J = 8.7 Hz), 4.37 (q, 2H, OCH 2 CH 3 , 3 J = 7.1 Hz), 1.39 (t, 3H, OCH 2 CH 3 , 3 J = 7.1 Hz), 0.26 (s, 9H, Si(CH 3 ) 3 ). 13 C NMR (CDC13, 125 MHz): δ = 166.4, 132.2, 130.4, 129.7, 128.0, 104.5, 98.0, 61.5, 14.7, 0.20. HiRes MS (ESI-TOF): Calcd. for [M + H] + C 4 H 19 O 2 Si + m/z = 247.1149; found m/z = 247.1147. (see, e.g., Fig. 7).

[00103] S3: K 2 CO 3 (0.426 g, 3.044 mmol) was added to a solution of S2 (0.250 g, 1.01 mmol) in MeOH (10 mL) and stirred at room temperature for 2 h. The solid material was isolated by filtration and the solvent was removed in vacuo. The residue was then dissolved in CH 2 Cl 2 (5 mL) before being washed with H 2 O (3 mL x 2) and brine (3 mL). The organic phase was then dried (Na2SO4). The solvent was removed in vacuo. Column chromatography (SiO 2 : Hexanes / CH 2 Cl 2 = 3: 1) afforded the product S3 as a white solid (0.180 g, 94%). IH NMR (500 MHz, CDC13): δ = 7.97 (d, 2H, Ar-H a , 3 J = 8.7 Hz), 7.54 (d, 2H, Ar-H b , 3 J = 8.7 Hz), 3.92 (s, 3H, OCH 3 ), 3.23 (s, I H, CDCH). 13 C NMR (CDCl 3 , 125 MHz): δ = 166.3, 131.9, 130.0, 129.3, 126.6, 82.7, 79.9, 52.1. HiRes MS (ESI-TOF): Calcd. for [M + H] + C 10 H 9 O 2 + = 161.0597; found m/z = 161.0590. (see, e.g., Fig. 8). [00104] S5: In a flame-dried, 3-neck, round bottom flask, S4 (2) (2.80 g, 3.62 mmol) and 2,5-dibromohydroquinone (0.973 g, 3.63 mmol) were dissolved in DMF (180 mL). Cs 2 CO 3 (2.37 g, 7.26 mmol) was added to the solution. The mixture was stirred under Ar at 90 0 C for 3 days. The solvent was then removed in vacuo. The residue was \dissolved in CH 2 CI 2 (100 mL) before being washed with brine (50 mL x 3). The organic phase was dried (Na 2 SO 4 ) and the solvent was then removed in vacuo. Column chromatography (SiO 2 : Et2O / CH 2 CI 2 = 2: 1) provided the product S5 as a white solid (0.650 g, 26%). 1 H NMR (500 MHz, CDCl 3 ): δ = 7.07 (s, 2H, Ar-HQl), 6.74 (s, 4H, Ar-HQ2), 4.05-3.68 (m, 32H, OCH 2 O). 13 C NMR (CDCl 3 , 125 MHz): δ = 153.1 , 150.3, 1 19.1 , 115.6, 11 1.4, 71.1 , 71.0,

70.9, 70.9, 70.8, 70.3, 69.8, 69.6, 68.2. HiRes MS (ESI-TOF): Calcd. for [M + H] + C 28 H 39 Br 2 Oi 0 + m/z = 693.0904; found m/z = 693.0902. (see, e.g., Fig. 9). [00105] S6: S5 (0.100 g, 0.144 mmol) and S3 (0.0510 g, 0.317 mmol) were dissolved in a mixture of DMF (3 mL) and iPr2NH (1 mL). Under Ar protection, Pd(PPh 3 ) 2 CI 2 (0.010 g, 0.014 mmol) and CuI (0.003 g, 0.014 mmol) were added to the solution. The mixture was stirred under Ar at 90 0 C for 48 h before the solvent was removed in vacuo. The residue was then dissolved in CH 2 Cl 2 (5 mL) before being washed with H 2 O (3 mL x 2) and brine (3 mL). The organic phase was dried (Na 2 SO,)) and the solvent was then removed in vacuo. Column chromatography (SiO 2 : Et 2 O / CH 2 C12 = 2: 1 ) provided product S6 as a yellow fluorescent solid (0.101 g, 84.0%). I H NMR (500 MHz, CDC13): δ = 8.02 (d, 4H, Ar-H a , 3 J = 8.2 Hz), 7.60 (d, 4H, Ar-H b , 3 J = 8.2 Hz), 7.00 (s, 2H, Ar-HQl ), 6.68 (s, 4H, Ar-HQ2), 4.13-3.64 (m, 32H, OCH 2 O), 3.94 (s, 3H, OCH 3 ). 13 C NMR (CDC13, 125 MHz): δ = 166.4, 153.7, 152.9, 131.4, 129.4, 129.4, 127.9, 117.0, 115.3, 94.5, 88.7, 71.0, 70.9, 70.7, 70.6, 69.6, 69.6, 69.5, 68.0, 52.1. HiRes MS (ESl-TOF): Calcd. for [M + H] + C 48 H 53 Oi 4 + m/z = 853.3430; found m/z = 853.3433. (see, e.g., Fig. 10).

[00106] 2: S6 (200 mg, 0.235 mmol) and KOH (52.6 mg, 0.939 mmol) were dissolved in a mixture of MeOH (10 mL), CH 2 Cl 2 (10 mL), and THF (10 mL). The following reaction and purification procedures are identical with those for 1. Product 2 is a yellow solid (181 mg, 94%). I H NMR (500 MHz, CDC13): δ = 13.24 (b, 2H, COOH), 8.04 (d, 4H, Ar-H a , 3 J = 8.3 Hz), 7.58 (d, 4H, Ar-H b , 3 J = 8.3 Hz), 6.99 (s, 2H, Ar-HQl), 6.67 (s, 4H, Ar-HQ2), 4.13-3.63 (m, 32H, OCH2O). 13 C NMR (CDC13, 125 MHz): δ = 170.2, 153.9, 153.0, 131.6, 130.1, 128.8, 128.7, 117.2, 115.5, 94.6, 89.2, 71.1, 71.0, 70.8, 70.7, 69.8, 69.7, 69.6, 68.1. HiRes MS (ESI-TOF): Calcd. for [M + H] + C 46 H 49 O,/ m/z = 825.3117; found m/z = 825.3115. (see, e.g., Fig. 11).

[00107 ] S8: A solution of 2,5-dibromohydroquinone (9.38 g, 35.0 mmol) and K 2 CO 3 (19.34 g, 140 mmol) in MeCN (400 mL) was heated under reflux in an inert atmosphere for 30 min. A solution of S7 (26.9 g, 77.0 mmol) in MeCN (40 mL) was added to the mixture dropwise over 30 min. Stirring and heating were continued for 3 days. The reaction mixture was then filtered and solvent was removed in vacuo. The residue was purified by column chromatography (SiO 2 : MeOH / CH 2 Cl 2 = 1 :9) to yield compound S8 as a white solid (13.7 g, 63%). 1 H NMR (500 MHz, CDC13): δ = 7.14 (s, 2H, Ar-H), 4.13 - 3.57 (m, 32H, OCH 2 O), 2.72 (b, 2H, OH). 13 C NMR (CDC13, 125 MHz): δ = 150.4, 1 19.3, 1 1 1.6, 72.7,

71.3, 70.8, 70.8, 70.5, 70.3, 69.8, 61.9. HiRes MS (ESI-TOF): Calcd. for [M + H] + C 22 H 37 Br 2 O 10 + m/z = 619.0748; found m/z = 619.0753. (see, e.g., Fig. 12). [00108] S9: S8 (3.10 g, 5.00 mmol), S3 (1.76 g, 1 1.0 mmol), Pd(PPh 3 ) 4 (289 mg, 0.250 mmol), and CuI (47.5 mg, 0.25 mmol) were added to Et3N (50 mL) and DMF (50 mL). The mixture was stirred at 80 0 C for three days before solvents were removed in vacuo. The residue was then dissolved in CH 2 Cl 2 (50 mL), Et3N (7.0 mL, 50.mmol), and 4- dimethylaminopyridine (122 mg, 1.0 mmol), and a solution of p-toluenesylfonyl chloride (2.29 g, 12.0 mmol) in CH 2 Ch (5 mL) was added. The solution was stirred for 3 h, washed with I M HCl (100 mL) and H 2 O (100 mL x 2), and then dried (MgSO4). The solvent was then removed in vacuo and the residue was purified by column chromatography (SiO 2 : EtOAc / CH 2 Cl 2 = 1 :2) to yield S9 as a yellow solid (2.72g, 50%). 1 H NMR (500 MHz, CDC13): δ = 8.02 (d, 4H, Ar-H a , 3 J = 8.4 Hz), 7.78 (d, 4H, Ar-H Ts" ', 3 J = 8.2 Hz), 7.58 (d, 4H, Ar-H b , 3 J = 8.3 Hz), 7.31 (d, 4H, Ar-HTs-2, 3 J = 8.2 Hz), 7.06 (s, 2H, Ar-H 0 ), 4.22-3.56 (m, 32H, OCH 2 O), 3.93 (s, 6H, COOCH 3 ), 2.42 (s, 6H, Ts-CH3). 13C NMR (CDCI3, 125 MHz): δ = 165.5, 152.7, 143.8, 131.9, 130.4, 128.8, 128.6, 128.5, 126.9, 126.9, 116.2, 113.0, 93.5, 87.7, 70.1, 69.7, 69.7, 69.5, 68.7, 68.5, 68.2, 67.6, 51.3, 20.6. HiRes MS (ESI- TOF): Calcd. for [M + H] + C 56 H 63 Oi 8 S 2 + m/z = 1087.3450; found m/z = 1087.3477. (see, e.g., Fig. 13).

[00109] Synthesis of BPP34C10DME SlO: A solution of S8 (1.09 g, 1.0 mmol), hydroquinone (110 mg, 1.0 mmol), and Cs2CO 3 (1.3 g, 4.0 mmol) in DMF (100 mL) was stirred and refluxed under inert atmosphere for 5 days. The reaction mixture was filtered and the solvent was removed. The residue was purified by column chromatography (SiO 2 : Et 2 O / CH 2 Cl 2 = 1 : 1 ) to yield S lO as a yellow solid (200 mg, 24%). (see, e.g., Fig. 14). ' [00110] Sl 1 : A solution of S9 (820 mg, 0.755 mmol), 1,5-dihydroxynaphthalene (121 mg, 0.755 mmol), and Cs 2 CO 3 (984 mg, 3.02 mmol) were dissolved in DMF (80 mL). The solution was heated under reflux and stirred in an inert atmosphere for 3 days. The reaction mixture was filtered and the solvent was removed. The residue was purified by column chromatography (SiO 2 : Et 2 O / CH 2 CI 2 = 1 :1) to yield SI l as a bright yellow solid (136 mg, 20%). 1 H NMR (500 MHz, CDC13): δ = 8.01 (d, 4H, Ar-H\ 3 J = 8.4 Hz), 7.78 (d, 2H, Ar- H 4/8 , 3 J = 8.4 Hz), 7.57 (d, 4H, Ar-H b , 3 J = 8.4 Hz), 7.23 (t, 2H, Ar-H 3/7 , 3 J = 8.4 Hz), 6.84 (s, 2H, Ar-H 0 ), 6.66 (d, 2H, Ar-H 2/6 , 3 J = 8.4 Hz) 1 4.18-3.69 (m, 32H, OCH 2 O), 3.94 (s, 6H, CH 3 ). 13 C NMR (CDCI3, 125 MHz): δ = 166.6, 154.2, 153.5, 131.5, 129.5, 129.4, 128.0, 126.6, 125.0, 1 16.6, 1 14.5, 1 13.7, 105.5, 94.4, 88.9, 71.0, 71.0, 70.9, 70.8, 69.7, 69.6, 68.2,

67.8, 52.3. HiRes MS (ESI-TOF): Calcd. for [M + H] + C 52 H 55 Oi 4 + m/z = 903.3586; foiind m/z = 903.3604. (see, e.g., Fig. 15).

[00111] 3: SI l (130 mg, 0.144 mmol) and KOH (80 mg, 1.4 mmol) were dissolved in a mixture of MeOH (2.5 mL) and CH 2 Cb (2.5 mL). The solution was stirred overnight. The reaction mixture was then filtered and the solvent was removed. The residue was purified by column chromatography (SiO 2 : CH 2 CI 2 / MeOH /AcOH = 9: 1 :0.01) to yield strut 3 as a bright yellow solid (121 mg, 96%). 1 H NMR (500 MHz, CD 3 SOCD3): δ = 12.8 (b, 2H, COOH), 7.94 (d, 4H, Ar-H a , 3 J = 8.4 Hz), 7.61 (d, 2H, Ar-H 4/8 , 3 J = 8.3 Hz), 7.60 (d, 4H, Ar- H b , 3 J = 8.4 Hz), 7.22 (t, 2H, Ar-H 3/? , 3 J = 8.3 Hz), 7.09 (s, 2H, Ar-H 0 ), 6.72 (d, 2H, Ar-H 2 ' 6 , 3 J = 8.3 Hz), 4.10-3.53 (m, 32H, OCH2O). 13 C NMR (CD3SOCD3, 125 MHz): δ = 172.3, 154.1 , 153.5, 131.7, 130.9, 129.9, 127.2, 126.3, 125.5, 116.8, 1 14.1 , 113.4, 106.1 , 94.7, 89.2, 70.6, 70.5, 70.4, 70.3, 69.3, 69.3, 69.2, 68.1. HiRes MS (ESI-TOF): Calcd. for [M + H] + C 50 H 51 O 14 + m/z = 875.3273; found m/z = 875.3250. (see, Fig. 16). [00112] 15 N-Labeled PQT 2PF6: Under inert atmosphere, CH 3 I (4.67 g, 32.9 mmol) was added dropwise to l5 N-labeled C O H 5 N (2.00 g, 25.3 mmol). The mixture was stirred at 50 0 C for 12 h before MeOH (0.5 mL) was added. The mixture was stirred for another 10 min before the solvents were removed in vacuo. The resulting white solid was dissolved in a mixture of EtOH (8 mL), MeOH (8 mL) and H 2 O (8 mL) together with NaCN (3.05 g, 63.2 mmol) and NaOH (1.21 g, 30.3 mmol). The solution was heated under reflux for 30 min. A dark blue solution resulted. After the solution had cooled to room temperature, ZnSO 4 -7H 2 O (10.2 g, 35.4 mmol) was added. A precipitate started to form. The mixture was kept at room temperature without stirring for 1 h before the precipitate was removed by filtration. The pH of the filtrate was then adjusted to 5 with H 2 SO 4 . O 2 was then bubbled into the solution for 12 h while the temperature of the solution was controlled under 50 0 C. The color of the solution turned from violet to tan. A saturated aqueous solution OfNH 4 PFo was then added until no more precipitate formed. The precipitate was collected by filtration, washed with H2O, EtOH and Et 2 O, and then dried in air. The product (3.90 g, 70%) is a white solid. 1 H NMR (500 MHz, CD3COCD3): δ = 9.39 (d, 4H, α-H, 3 J = 6.5 Hz), 8.86 (d, 4H, β-H, 3 J = 6.5 Hz), 4.76 (s, 6H, CH 3 ). 13 C NMR (CD3COCD3, 125 MHz): δ = 151.5, 146.5, 126.7, 52.2. HiRes MS (ESI-TOF): Calcd. for [M PFO] + C 12 H 14 F 6 N 2 P + m/z = 331.079; found m/z = 331.082. (see, e.g., Fig. 17).

[00113] [PQTc2] 2PF 6 single crystal: Strut 2 (9.01 mg) and PQT 2PF 6 (3.54 mg) were dissolved in Me 2 CO (5 mL) in a 20-mL vial. n-Pentane was added to the solution until

some precipitate was observed. The mixture was filtered to obtain a saturated solution. The solution was left at room temperature for 3 days. Red block-shaped crystals were observed on the wall of the vial.

[00114 ] MOF-1000: A solid mixture of strut 1 (17.00 mg, 3.99 x 10 "5 mol) and Zn(NO 3 ) 2 -4H 2 O (12.00 mg, 4.59 x 10 "5 mol) was dissolved in N,N-diethylformamide (DEF, BASF Corporation) (1 mL) in a 4-mL vial. The vial was capped and placed in an isothermal oven at 85 0 C for 48 h. The vial was then removed from the oven and allowed to cool to room temperature naturally. Colorless block crystals were collected and rinsed with fresh DEF (4 x 1 mL). Elemental Analysis (evacuated): Zn 4 O(C 26 H 16 Oe) 3 : Calcd.: C, 60.41%; H, 3.12%. Found: C, 59.39%; H, 3.43%.

[00115] BORG-I : Methylamine solution (40 wt. % in H 2 O, Aldrich Chemical Co.) (50 μL) was mixed with N,N-dimethylformamide (DMF, Fisher Scientific International Inc) (2 mL) as stock solution A. A solid mixture of strut 2 (3.60 mg, 4.36 x 10 "6 mol) and Zn(NO 3 ) 2 4H 2 O (5.25 mg, 2.01 x 10 "5 mol, EM Science) was dissolved in DMF (1.0 mL) in a 4-mL vial. Stock solution A (20 μL) was added to the vial. The vial was capped and placed in an isothermal oven at 65 0 C for 24 h. The vial was then removed from the oven and allowed to cool to room temperature naturally. After removal of mother liquor from the mixture, fresh DMF was added to the vial. Light yellow cubic crystals of BORG-I were collected and rinsed with DMF (4 x 1 mL). Elemental Analysis (evacuated): Zn 4 O(C 46 H 46 O M ) 3 : Calcd.: C, 60.36%; H, 5.07%. Found: C, 59.49%; H, 5.07%. BORG- i A: A solid mixture of strut 2 (3.30 mg, 4.00 x 10 "6 mol) and Zn(NO 3 ) 2 -4H 2 O (5.25 mg, 2.01 x 10 "5 mol, EM Science) was dissolved in DMF (1.0 mL) in a 4-mL vial. Stock solution A (20 μL) was added to the vial. The vial was capped and placed in an isothermal oven at 65 0 C for 24 h. The vial was then removed from the oven and allowed to cool to room temperature naturally. After removal of mother liquor from the mixture, fresh DMF was added to the vial. Occasionally, a mixture of light yellow cubic crystals and light yellow hexagonal crystals was collected. The hexagonal shaped crystals were picked and single crystal X-ray diffraction determined the structure of BORG-I A. (Adding less than 2 mg PQT-2PF6 could avoid the formation of BORG-IA under these conditions.)

[00116] BORG-2: A methylamine solution (40 wt. % in H2O) (50 μL) was mixed with 2 mL DMF as stock solution A. A solid mixture of strut 3 (3.82 mg, 4.36 x 10 "6 mol) and Zn(NO 3 ) 2 -4H 2 O (5.25 mg, 2.01 x 10 "5 mol) was dissolved in DMF (1.0 mL) in a 4-mL vial. Stock solution A (20 μL) was added to the vial. The vial was capped and placed in an

isothermal oven at 65 0 C for 24 h. The vial was then removed from the oven and allowed to cool to room temperature naturally. After removal of mother liquor from the mixture, fresh DMF was added to the vial. Light yellow cubic crystals of BORG-2 were collected and rinsed with DMF (4 x 1 mL). Elemental Analysis (evacuated): Zn 4 O(CSoH 4 SOi 4 )3: Calcd.: C, 62.20%; H, 5.01%. Found: C, 63.21%; H, 4.98%. BORG-I Pseudorotaxanes: BORG-I crystalline solid (approximately 20 mg) in fresh DMF was exchanged with fresh Me 2 CO (10 mL) for 3 days, three times every day, to remove unreacted starting material. After decanting the Me2CO, saturated PQT 2 PFO solution in Me 2 CO (5 mL) was added. The color of the crystals immediately turned red. After sitting for 6 h, the mixture was filtered and the red solids were flush-washed with Me 2 CO (10 mL). The solid was dried under vacuum (10 "2 Torr) for 24 h at room temperature. Elemental Analysis (evacuated): Zn 4 O(C 46 H 46 O H ) 3 (C 12 H 14 N 2 P 2 Fi 2 )S: Calcd.: C, 50.06%; H, 4.45%; N, 2.01%; F, 16.38%. Found: C, 49.46%; H, 4.50%; N, 1.83%; F, 14.46%.

[00117] As described above, crystals of MOF-1000 (Fig. 2A and 3A) were obtained by mixing a solution of strut 1 , with Zn(NO 3 ) 2 *4H 2 O, in diethylformamide (DEF) using conditions previously employed in the synthesis of MOF-5 (Eddaoudi et al, Science 295, 469 (2002); H. Li, M. Eddaoudi, M. O'Keeffe, O. M. Yaghi, Nature 402, 276 (1999)). Its crystal structure displays the same structural topology as does MOF-5. It is found to be four- fold interpenetrated because of the length and slender nature of the strut — the distance between the two carbon atoms from the carboxylate groups is 19.3 A. Successful crystallization of MOF-1000, however, confirmed the practicality of creating BORGs using this synthetic protocol.

[ 00118] The struts 2 and 3, containing 34- and 36-membered polyether rings, which have been extensively used as receptors for the wide range of electron-deficient substrates, are ideally suited as molecular recognition modules for making BORGs. Strut 2 was prepared by means of a convergent synthetic approach (as described above), and used under similar conditions to those employed in the synthesis of MOF- 1000 to give BORG-IA and BORG- 1. The crystal structure of BORG- 1 A is a triply interpenetrating framework (Fig. 2B and 3B), while that of BORG-I is the corresponding non-interpenetrating form (Fig. 2C and 3C); both have the MOF-5 type topology. The existence of BORG-I A, despite its occasional appearance as a minor product, validates indirectly the high porosity of BORG- 1. The sheer openness of the structure, however, led to optimize the reaction conditions yet further in order to successfully obtain BORG-I as a pure phase. BORG-I , which has an Fm-

3m symmetry, with a unit cell parameter a = 52.93 A, is the largest non-interpenetrating isoreticular MOF (IRMOF) ever characterized by crystallography. Furthermore, this methodology was extended to the synthesis of BORG-2 (Fig. 2D and 3D) by using the 1,5- dioxynaphthalene-containing strut 3, which was produced via a divergent synthetic route (as described above). Single crystal X-ray diffraction studies indicate that BORG-2 shares an identical cubic backbone with BORG-I , affirming the generality of such a methodology of building a variety of crystalline structures with such long struts capable of molecular recognition.

[00119] Calculations of the volumes of open space within the BORG structures confirm the highly open nature of these crystals (86.9 % space unoccupied by BORG-I framework atoms, based on a model using the program Cerius2, version 4.2). The inherent flexibility of the macrocyclic polyether substructure was evident from the single crystal X- ray analysis of BORG-I . The bismethylenedioxy units of the tetraethylene glycol loops in the substructure are found to be highly disordered. Nevertheless, the positions of all the atoms in the inorganic joints and the rigid backbone of the links are unambiguous as judged by comparison of the resulting bond distances and angles with the model structure. Based on the overall geometry and stoichiometry of the BORG framework, it was concluded that the crown ether receptors — capable of the complexation behavior required for molecular recognition — are integrated precisely and periodically inside a robust framework. Thus, the extended framework provides the basis for their strategic placement so that they are exposed to the maximum freedom of expression in three-dimensional space. [00120] Further evidence of complexation was obtained by examining the I H NMR spectrum of the digested BORG-I pseudorotaxanes solid. Integration of the peaks appearing at 7.96 ppm (d, 4H, Ar-H a in 2, see Fig. 4G) and 4.60 ppm (s, 6H, N-CH3 in PQT 2+ ) revealed the expected 1 : 1 ratio of strut 2 and the PQT 2+ dication, indicating that the docking phenomenon of the PQT 2+ dications does indeed take place at every crown ether ring throughout the whole BORG framework (Fig. 14). Solid-state 15N NMR spectroscopy, a technique which is highly sensitive to the environment of the nitrogen ( 15 N) in the PQT 2+ dication, provided further strong evidence for docking in BORG-I . Isotope-labeled PQT 2+ with 25% abundance of 15N was used to make the BORG-I pseudorotaxanes and the solid was examined by 15N cross-polarization magic-angle spinning (CP/MAS) spectroscopy. The spectrum of the uncomplexed PQT2+ dication has a 15 N signal centered on 207.2 ppm, while the spectrum of the PQT 2+ dication, bound within the crown ether rings in BORG-I ,

shows a significant upfield shift to 204.6 ppm for the 15N resonance resulting from docking into the macrocyclic polyether units of the struts (Fig. 4, D to F). [00121] Similar studies carried out on strut 2 were used as a molecular model for comparison with BORG-I complexation experiments. Here, addition of PQT«2PFδ to a Me2CO solution of strut 2 led to the formation of a pseudorotaxane [PQTc2] « 2PF6. The binding affinity (Ka = 820 M) between the PQT 2+ dication and strut 2 in solution was obtained from spectrophotometric titrations. Single crystal X-ray diffraction of the [PQTc2] « 2PF 6 (Fig. 41) clearly shows the insertion of the Fϊ-electron deficient bipyridinium dication through the middle of the macrocyclic polyether. FI - FI Stacking aided and abetted by [C--η «« O] interactions are reflected in the interplanar separation of 3.6 A between the bipyridinium unit Of PQT 2+ and the hydroquinone rings. The same upfield shift trend in the 15N NMR spectra observed for BORG- I pseudorotaxanes was also evident in the 15N NMR spectra of [PQTc=2] « 2PF 6 in the solid state (Fig. 4H) as well as in solution. Control experiments were carried out by attempting to introduce PQT « 2PF6 into porous MOF- 177 crystals, the pore dimensions of which were expected to allow the free movement of the PQT 2+ dications within the pores. It was determined that less than 0.06 PQT 2+ dications per strut of MOF-177 were incorporated in the pores. These results show that specific stereoelectronic host-guest interactions, rather than just simple diffusion and adsorption, are responsible for the all but quantitative formation of the BORG-I pseudorotaxanes. [ 00122 ] UV / visible Absorption and Fluorescence Studies of Strut 2 and the Pesudorotaxane |PQTc2|-2PF6: UV / visible spectroscopy was performed on an Agilent 8453 Spectroscopy System. Emission spectra were recorded on a coupled charge device (CCD) through a SpectraPro 230Oi 0.300 m imaging Triple Grating monochromator / spectrograph, excited by a 377 nm / 16 mW laser.

[ 00123 ] Measurement of the Binding Constant of PQT 2PF 6 and Strut 2 by Spectrophoto-metric Titration:

Table 1. The charge-transfer absorptions at 435 nm of the pseudorotaxane [PQTc2] -2PF O in eight samples of differing concentrations.

[00124] The concentration of strut 2 was set at 0.500 mM in all samples. The various concentrations of PQT-2PF6 were added and the corresponding absorptions were measured

with UV / vis spectrometry. δA is the absolute absorption corrected using a blank control sample ([PQT-2PF6] = 0).

[00125] The binding constant was obtained by computer fitting (Fig. 19) of the experimental absorbance values to the following equation (J): where AA is the absorbance of the charge-transfer complex measured at a host concentration [2]0 = 0.500 mM and a guest concentration [PQT], b is the optical path length (1 cm), δε is the molar absorptivity of the charge-transfer complex, and K is the equilibrium constant for the formation of the complex. The experimental data points were consistent with 1 : 1 stoichiometry for all the complexes.

[00126] Solution NMR Spectroscopic Studies of the Pseudorotaxane [PQTc2]-2PF 6 : 15 N-labeled paraquat bishexafluorophosphate (PQT-2PF 6 ) (8.7 mg, 0.018 mmol) and strut 2 (5.0 mg, 0.006 mmol) were dissolved in CD 3 COCD 3 (0.5 mL). 1 H, 13 C, 1 5 N, 1 H- 1 H COSY, and 1 H- 13 C HMQC NMR experiments were conducted at room temperature and lowered temperatures.

[00127] Solid-State 13C and 15N CP/MAS NMR Spectroscopic Studies of BORG-I and BORG-I Pseudorotaxanes.

[00128] Solid-State 13C CP/MAS and 15 N CP/MAS nuclear magnetic resonance spectroscopy High resolution solid-state nuclear magnetic resonance (NMR) spectra were recorded at ambient pressure on a Bruker DSX-300 spectrometer using a standard Bruker magic-angle spinning (MAS) probe with 4 mm (outside diameter) zirconia rotors. The magic angle was adjusted by maximizing the number and amplitudes of the signals of the rotational echoes observed in the 79 Br MAS FID signal from KBr. Cross-polarization with

MAS (CP/MAS) was used to acquire 13C data at 75.47 MHz. The 1 H and 13 C ninety-degree pulse widths were both 4 ms. The CP contact time was 3 ms. High power two-pulse phase modulation (TPPM) 1 H decoupling was applied during data acquisition. The decoupling frequency corresponded to 72 kHz. The MAS sample-spinning rate was 10 kHz. Recycle delays varied from 3 to 30 s, depending upon the compound as determined by observing no apparent loss in the 13C signal from one scan to the next. The 13C chemical shifts are given relative to tetramethylsilane as zero ppm, calibrated using the methine carbon signal of adamantane assigned to 29.46 ppm as a secondary reference.

[00129] CP/MAS was also used to acquire 15 N data at 30.41 MHz. The CP contact time was 3 ms at ambient temperature. High power two-pulse phase modulation (TPPM) 1 H decoupling was applied during data acquisition. The decoupling frequency corresponded to 72 kHz.

[00130] The MAS sample-spinning rate was 5 kHz. The recycle delay time was 3 s, which was determined from the 13 C CP/MAS experiments. The 15 N chemical shifts were externally referenced with l5 N-glycine (32.6 ppm versus liquid NH3 at 25 0 C). In the variable temperature experiment, the temperature calibration was performed using the 207Pb resonance Of Pb(NOs) 2 . The CP contact time varied from 3 to 5 ms, depending upon the temperature.

[00131] Solid-State 15N CP/MAS Nuclear Magnetic Resonance Spectroscopy of [PQTc2]-2PF6. Strut 2 and PQT2PF 6 (isotope labeled with 25% abundance of 15 N) with different mole ratios (1 :4, 1 :2, 1 : 1 , 2: 1) were dissolved in Me2CO. The color change of the solution (yellow to orange) indicated pseudorotaxane formation. The solvent was removed by evaporation and the solid was dried under vacuum (10 "2 Torr) for 4 h at room temperature.

[00132] Solid-State 15N CP/MAS Nuclear Magnetic Resonance Spectroscopy of BORG-I Pseudorotaxanes. Preparation of BORG-I Pseudorotaxanes (BORG-I: PQT-2PF 6 = 1:1): BORG-I crystalline solid (approximately 20 mg) in fresh DMF was exchanged with fresh Me2CO (10 mL) 3 times a day for 3 days. After Me2CO was decanted, saturated PQT 2 PF O (isotope labeled with 25% abundance of 15N) solution in Me 2 CO (5 mL) was added. The color of the crystals immediately turned red. After sitting for 6 h, the solid was isolated by filtration and flush-washed with Me 2 CO (10 mL). The solid was dried under vacuum (10 "2 Torr) for 24 h at room temperature.

[00133] Preparation of BORG-I Pseudorotaxanes (BPP34C10 in BORG-I: PQT-2PF 6 = 1.8:1, 1:1.8 and 1:2.5): BORG-I (about 10 mg) crystalline solid in DMF was exchanged with fresh Me2C0 (10 mL) 3 times a day for 3 days. After Me 2 CO was decanted, PQT- 2PF 6 (isotope labeled with 25% abundance of 15 N) solution in Me 2 CO (3 mL) was added. The amount of PQT- 2PF 6 varies from 6 mg to 22 mg in every sample. The crystals turned red. After sitting for 6h, the solid was isolated by filtration and dried under vacuum (10 "2 Torr) overnight at room temperature.

[00134] After the solid-state 15 N CP/MAS experiment, 10 mg of the sample was transferred to a NMR tube. The solid was digested with 5 drops of DCl (20% in D 2 O) and 0.5 mL DMSO-d6. The molar ratio of the strut and PQT 2PF 6 in each sample was determined by integration of peaks at 7.96 ppm (d, 4H 1 Ar-H a in 2, V= 8.5 Hz) and 4.60 ppm (s, 6H, N-CH 3 in PQT 2+ ) in 1 H solution NMR spectra.

[00135] Determination of PQT-2PF6 Loading in BORG-I and MOF-177 by IH NMR Spectroscopy PQT-2PF6 Diffusion in MOF-177: MOF-177 (about 10 mg) crystalline solid in DEF was exchanged with fresh Me2CO (10 mL) for 3 times a day for 3 days. After decanting the Me2CO, saturated PQT- 2PF 6 solution in Me 2 CO (5 mL) was added. After sitting for 6 h, the crystals were isolated by filtration and flush-washed with Me 2 CO (10 mL). The solid was dried under vacuum (10 ~2 Torr) for 24 h at room temperature. Determination of PQT-2PF 6 Loading by 1 H NMR: BORG-I pseudorotaxanes and PQT 2+ included MOF-177 were digested in a mixture of 0.5 mL CD 3 SOCD 3 and 0.1 mL DCl (20% in D 2 O). The ratio of strut 2 and PQT-2PF 6 in BORG-I pseudorotaxanes was determined by the integration of peaks of Ar-H a in 2 (d, 4H) and N-CH 3 in PQT 2+ (s, 6H) in 1 H solution NMR. The ratio of the strut 4,4',4"-benzene-l ,3,5-triyl-tribenzoic acid (H3BTB) and PQT 2+ in PQT 2+ -included MOF-177 was determined by the integration of peaks of Ar- H in H 3 BTB ( 15 H) and N-CH 3 in PQT 2+ (s, 6H) in I H solution NMR. Peak positions may vary in every experiment depending on the amount of DCl in the system. [00136] Single Crystal X-Ray Diffraction Data Collection, Structure Solution and Refinement Procedures. Data were collected on a Bruker SMART APEXII three circle diffractometer equipped with a CCD area detector and operated at 1200 W power (40 kV, 30 mA) to generate Cu Ka radiation (λ = 1.5418 A). The incident X-ray beam was focused and monochromated using Bruker Excalibur Gobel mirror optics. Crystals were mounted either on nylon CryoLoops (Hampton Research) with Paraton-N (Hampton

Research), or in flame sealed borosilicate capillaries containing a small amount of mother liquor to prevent desolvation during data collection.

[00137] Initial ω-φ scans of each specimen were taken to gain preliminary unit cell parameters and to assess the mosaicity (i.e. breadth of spots between frames) of the crystal to select the required frame width for data collection. For all cases frame widths of 0.5° were judged to be appropriate and full hemispheres of data were collected using the Bruker APEX2 software suite to carry out overlapping φ and ω scans at different detector (2θ) settings. Following data collection, reflections were sampled from all regions of the Ewald sphere to redetermine unit cell parameters for data integration and to check for rotational twinning using CELL NOW. Following exhaustive review of collected frames the resolution of the dataset was judged, and if necessary regions of the frames where no coherent scattering was observed were removed from consideration for data integration. Data were integrated using Bruker APEX2 V 2.1 software with a narrow frame algorithm and a 0.400 fractional lower limit of average intensity. Absorption corrections were ineffectual for improving the quality of data, which is not unexpected for small crystals of low density solids containing primarily light atoms. Space group determination and tests for merohedral twinning were carried out using XPREP (10). In all cases the highest possible space group was chosen and no indications of merohedral twinning were observed. [00138] All structures were solved by direct methods and refined using the SHELXTL '97 software suite. Atoms were located from iterative examination of difference F-maps following least-squares refinements of the earlier models. Final models were refined anisotropically (if the number of data permitted and stable refinement could be reached) until full convergence was achieved. Several structures contained disordered components within the structure. In these cases occupancies X and (1 - X) and equivalent displacement parameters were assigned to each pair of atoms in the disordered groups and X was refined as an independent free variable. Some atoms could not be located precisely due to high disorder (atoms in crown ethers in BORG-I, BORG-I A etc.). Hydrogen atoms were placed in calculated positions and included as riding atoms with isotropic displacement parameters 1.2 - 1.5 times f/eq of the attached carbon atoms. Modeling of electron density within the voids of the frameworks did not lead to identification of guest entities in all structures due to the lowered resolution of the data. This difficulty, which is typical of porous crystals that contain solvent filled pores, lies in the raw data where observed strong (high intensity) scattering becomes limited to ~1.0 A at best, with higher resolution data present but weak

(low intensity). As is a common strategy for improving X-ray data, increasing the exposure time of the crystal to X-rays did not ameliorate the quality of the high angle data in these cases, as the intensity from low angle data saturated the detector and minimal improvement in the high angle data was achieved. Additionally, diffuse scattering from the highly disordered crown ethers and solvents in the void spaces within the crystal and solvents from the capillary used to mount the crystal contributed to the background noise and the 'washing out' of high angle data. The only optimal crystals suitable for analysis were generally small and weakly diffracting, and unfortunately, larger crystals, which might improve the quality of the data, presented a lowered degree of crystallinity, and optimization of crystal growing conditions for large high-quality specimens has not yet been fruitful. For all extended framework structures it was also more reasonable to model against data collected at elevated temperatures (-50 to -15 0 C, rather than -120 to -100 0 C) when guest entities in the structures were allowed to move freely and therefore did not contribute coherent scattering terms to the observed structure factors. Conversely, at cryogenic temperatures it was found that free solvent in the crystal would "freeze" into non-ordered arrays within the pore structure. In such cases the modeling of the disordered guest entities becomes intractable and interferes with determination of the framework. Thus, electron density within void spaces which could not be assigned to any definite guest entity was modeled as isolated oxygen and carbon atoms, and the foremost errors in all the models lie with assignment of guest electron density. To prove the correctness of the atomic positions in the framework, the application of the SQUEEZE routine of A. Spek has been performed when applicable. However, atomic co-ordinates for the "non-SQUEEZE" structures have also been presented and the CIFs were also submitted for the cases where the program SQUEEZE has been employed. All structures were examined using the Adsym subroutine of PLATON to assure that no additional symmetry could be applied to the models. All ellipsoids in ORTEP diagrams are displayed at the 30% probability level unless noted otherwise. [00139] Experimental and Refinement Details for [PQTc2]-2PF 6 A red block shaped crystal (0.10 x 0.10 x 0.05 mm 3 ) of [PQTc2]-2PF6 coated with Paraton-N oil on a Cryo-Loop pin was mounted on a SMART APEXII three circle diffractometer equipped with a CCD area detector and operated at 1200 W power (40 kV, 30 mA) to generate Cu Ka radiation (λ = 1.5418 A) while being flash frozen to 100 K in a liquid N2 cooled stream of nitrogen. Full hemispheres of data were collected using the Bruker APEX2 software suite to carry out overlapping φ and ω scans at three different detector (2θ) settings (2θ = 28, 60,

100°). A total of 9915 reflections were collected, of which 4650 were unique and 3240 of these were greater than 2σ(/). The range of θ was from 2.41 to 44.1 1 °. Analysis of the data showed negligible decay during collection. The structure was solved in the triclinic λpace group with Z = 2 using direct methods. Atoms C40, O41 , C42, C43, C44 and C47 were found to be disordered and were refined with the occupancy for each group modeled as its own independent free variable (X, 1 - X). Two PF6- were found in the asymmetric unit, one of which was found to be disordered with half occupancy for each group. Two and a half acetone molecules were also found in every asymmetric unit. Due to the low data to parameter ratio, only P, O, N, some C and some F atoms were refined anisotropically. Hydrogen atoms were generated as spheres riding the coordinates of their parent atoms. A final ratio of 7.5 for reflections to parameters was achieved. Absorption correction was not performed. Final full matrix least-squares refinement on Fl converged to R\ = 0.0961 (F >2σ(F)) and wR2 = 0.2525 (all data) with GOF = 1.061. Table 3. Crystal data and structure refinement for [PQT<=2] 2PF 6 .

[00140] Experimental and Refinement Details for MOF-1000 A light yellow block shaped crystal (0.20 x 0.20 * 0.10 mm 3 ) of MOF-1000 was placed in a 0.4 mm diameter borosilicate capillary along with a small amount of mother liquor. The capillary was flame sealed and mounted on a SMART APEXII three circle diffractometer equipped with a CCD area detector and operated at 1200 W power (40 kV, 30 mA) to generate Cu Ka radiation (λ = 1.5418 A) while being cooled to 258(2) K in a liquid N2 cooled stream of nitrogen. After a preliminary unit cell parameters check, the data collection strategy for MOF-1000 was refined by the APEX2 software suite according to the desired completeness

and redundancy (desired completeness: 100%, desired redundancy: 4). In total, 5053 frames were collected under the strategy of overlapping φ and ω scans at different detector (2θ) settings in 53 hours. Exhaustive reviewing of collected frames showed the unit cell parameters change gradually during the data collection. Table 4 shows that different unit cell parameters were obtained when frames from different time segments were selected. Data from two other crystals from different batches were collected at different temperatures 258 and 233 K), and similar change was observed. No clear pattern for the change in unit cell parameters was observed. In order to achieve better structure determination and refinement, only data from the first 28 hours was used, which shows less inconsistency in the unit cell parameters. A total of 124606 reflections were collected, of which 49574 were unique and 31233 of these were greater than 2σ(7). The range of θ was from 1.67 to 45.13°. The program Scale was performed to minimize differences between symmetry-related or repeated reflections.

Table 4. Different unit cell parameters were obtained when frames from different time segments were selected for MOF-1000.

[00141] The structure was solved in the triclinic Pl space group with Z = I using direct methods. All non- hydrogen atoms were refined isotropically with hydrogen atoms generated as spheres riding the coordinates of their parent atoms. The center benzene ring and methoxy groups show a high degree of disorder due to the length of the strut. MOF- 1000 contains three struts per Zn4O secondary building unit. In every Zn 4 O secondary unit, one zinc atom is octahedral, to which two diethylformamide molecules are bonded in addition to four oxygen atoms, while the three other zinc atoms are tetrahedral. Due to the low data quality and the inconsistent unit cell parameters during the data collection, only some of the diethylformamide molecules can be located, while others show only parts of diethylformamide molecules. The attempts made to model solvent molecules did not lead to identification of guest entities in all structures. Since the solvent is not bonded to the

framework, this can be expected for the MOF structures. Very high displacement parameters, high esd"s and partial occupancy due to the disorder make it impossible to determine accurate positions for solvent molecules. Nonetheless, assignment and refinement of the framework of MOF-1000 were unambiguous. Given the magnitude of MOF-1000, the porosity, and the population with highly disordered guest molecules, the final refined structures have, expectedly, elevated reliability factors compared to those from small molecule crystallography. The structure was reported to display the framework of MOF- 1000 as isolated in the crystalline form. The structure is a 4-fold interpenetrating primitive - cubic framework. To prove the correctness of the atomic positions in the framework, the application of the SQUEEZE routine of A. Spek has been performed. However atomic coordinates for the "non-SQUEEZE" structures are also presented. The program SQUEEZE failed when all the atoms were included due to the huge number of atoms in the unit cell. Solvents coordinated to the Zn4O clusters and all hydrogen atoms were removed before the SQUEEZE routine. Thus the structure reported after SQUEEZE does not include any hydrogen atoms and solvents. Final full matrix least-squares refinement on Fl converged to R] = 0.1030 (F >2σ(F)) and wRl = 0.2996 (all data) with GOF = 1.000. For the structure where the SQUEEZE program has not been employed, final full matrix least-squares refinement on Fl converged to R] = 0.2046 (F >2σ(F)) and wRl = 0.5392 (all data) with GOF = 1.972.

[00142 ] Experimental and Refinement Details for BORG-IA A light yellow hexagonal shaped crystal (0.30 * 0.30 x 0.10 mm3) of BORG-I A was placed in a 0.5 mm diameter borosilicate capillary along with a small amount of mother liquor. The capillary was flame sealed and mounted on a SMART APEXII three circle diffractometer equipped with a CCD area detector and operated at 1200 W power (40 kV, 30 mA) to generate Cu Ka radiation (λ = 1.5418 A) while being cooled to 258(2) K in a liquid N2 cooled stream of

nitrogen. Full hemispheres of data were collected using the Bruker APEX2 software suite to carry out overlapping φ and ω scans at three different detector (2θ) settings (2θ = 28, 60, 100°). A total of 35903 reflections were collected of which 5845 were unique and 4142 of these were greater than 2σ(/). The range of θ was from 1.44 to 42.62°. Analysis of the data showed negligible decay during collection. The program Scale was performed to minimize differences between symmetry related or repeated reflections.

[00143] The structure was solved in the trigonal /"space group with Z = 6 using direct methods. All non-hydrogen atoms in the backbone of the framework were refined anisotropically with hydrogen atoms generated as spheres riding the coordinates of their parent atoms. Due to the highly porosity of the BORG-IA structure, bisparaphenylene-[34]- crown-10 (BPP34C10) crown ethers were surrounded by all the guest entities. Even though the crown ether was chemically bonded to the backbone of the link, the macrocycle with 34 atoms shows extremely flexibility in the uncomplexed form and there can be many conformations. Several disordered atoms were located from macrocycles (Ol 1 , C 12, C 13, O13, C14, O60, C61 , C62, O62, C63 and O64), and stable isotropic refinement was achieved. Macrocycle atoms relatively far away from the backbone have higher displacement parameters, indicating an elevated degree of disorder, probably including both static disorder and dynamic disorder. Attempts to determine the positions of hydroquinone rings and other bismethylenedioxy units of the tetraethylene glycol loops in the crown ethers did not lead to positive identification due to the highly disordered crown ether with limited periodicity. The attempts made to model solvent molecules did not lead to identification of guest entities. Since the solvent is not bonded to the framework, this can be expected for the BORG structures. Very high displacement parameters, high esd's and partial occupancy due to the disorder made it impossible to determine accurate positions for solvent molecules. Nonetheless, assignment and refinement of the backbone framework and partial crown ether segments of BORG-IA was unambiguous, as judged by the resulting bond and angle metrics. Given the magnitude of BORG-IA, its high porosity, and population with highly disordered crown ethers and guest molecules, the final refined structure has, expectedly, elevated reliability factors compared to those from small molecule crystallography.

[00144] The structure was reported to display the backbone framework and partial crown ether segments for BORG-IA as isolated in the crystalline form. BORG-IA contains three links per Zn4O secondary building unit. The structure is a 3-fold interpenetrating

cubic framework with centers of their SBUs aligned along the body diagonal of the cube. To prove the correctness of the atomic positions in the framework the application of the SQUEEZE routine of A. Spek has been performed, and both backbone frameworks and partial ethylene glycol segments have been included. However atomic co-ordinates for the "non-SQUEEZE" structures are also presented. Final full matrix least-squares refinement on Fl converged to Rl = 0.0780 (F>2σ(F)) and wR2 = 0.2271 (all data) with GOF = 1.036. For the structure where the SQUEEZE program has not been employed, final full matrix least-squares refinement on Fl converged to Rl = 0.1449 (F>lσ(F)) and wR2 = 0.4189 (all data) with GOF = 1.792. When only framework atoms were included in the latter structure factor calculation, the residual electron density in the F-map was located within the pores of BORG-I A.

[00145] The empirical formula from crystal structure refinement is C 2 0HgO 5 . 17 Zn 1.33 , with a density of 0.396 g cm '3 . This model only contains parts of crown ether segments. If all the atoms in the framework are considered, the calculated empirical formula is C 4 6H46θi4.33Znι 33, with a density of 0.739 g cm '3 .

[00146] Experimental and Refinement Details for BORG-I A light yellow cubic crystal (0.45 * 0.45 * 0.45 mm 3 ) of BORG-I was placed in a 0.6 mm diameter borosilicate capillary along with a small amount of mother liquor. The capillary was flame sealed and mounted on a SMART APEXII three circle diffractometer equipped with a CCD area detector and operated at 1200 W power (40 kV, 30 mA) to generate Cu Ka radiation (λ = 1 5418 A) while being cooled to 258(2) K in a liquid N2 cooled stream of nitrogen. After a preliminary unit cell check of parameters, the data collection strategy for BORG-I was

refined by the APEX2 software suite for the desired completeness and redundancy (desired completeness: 100%, desired redundancy: 4). In total, 2591 frames were collected with overlapping φ and ω scans at different detector (2θ) settings. A total of 57237 reflections were collected, of which 1508 were unique and 1098 of these were greater than 2σ(/). The range of θ was from 1.45 to 33.90°. Analysis of the data showed crystal decomposition during collection due to solvent loss. Linear dependence of the frame number on crystal decomposition was counted by B-value refinement when the program Scale was performed by the APEX2 software.

[00147 ] The structure was solved in the cubic Fm3m space group with Z = 8 using direct methods. ZnI , Zn2, 01 , O2, O3, Cl , C5 and C6 have been refined anisotropically, while other non-hydrogen atoms that could be located have been refined isotropically, with hydrogen atoms generated as spheres riding the coordinates of their parent atoms. Zinc and carboxyl oxygen atoms in inorganic building blocks were disordered over two sites respectively. Relative occupancy was fixed during the refinement to avoid correlation with displacement parameters. These optimized occupancy values were assigned by making the anisotropic Uij components of the atoms in the two parts approximately within the same range. In addition, the phenylene rings connected to carboxyl groups were refined as disordered over two sites with equal occupancy. It was assumed that the rotational energy barrier of the center phenylene ring moiety could be low and might have many conformers with various dihedral angles between the center phenylene ring and phenylene rings on either side. Thus severe disorder in the center phenylene ring was also expected, and this allowed a more severe disorder of the tetraethylene glycol loops in the uncomplexed crown ethers. As a result, high displacement parameters for atoms from the center phenyl ring (C8, C9) were to be expected. Hydrogen atoms were added as spheres riding the coordinates of C9, even though only half of the C9 atoms were bonded to hydrogen, while the other half of the C9 atoms were bonded to the tetraethylene glycol loops. Furthermore, due to the high porosity of the BORG-I structure (<a = 52.9345(7) A), crown ethers were surrounded by all the guest entities. Attempts to determine the positions of the hydroquinone rings and the other bismethylenedioxy units of the tetraethylene glycol loops in the crown ethers did not lead to positive identification due to the highly disordered crown ethers with limited periodicity in the highly porous structure. The attempts made to model the solvent molecules also did not lead to identification of the guest entities. Very high displacement parameters, high esd's and partial occupancy due to the disorder made it impossible to

determine accurate positions for the solvent molecules. Thus, electron density within void spaces which could not be assigned to any definite entity was modeled as isolated carbon atoms (CI S, C2S, C3S, C4S and C5S), and the foremost errors in all the models lay with assignment of crown ethers and guest electron density. Given the size of BORG-I , the high porosity, and population with highly disordered crown ethers and guest molecules, the final refined structures had, expectedly, elevated reliability factors compared to those from small molecule crystallography.

[00148] The structure was reported to display the backbone framework for BORG-I as isolated in the crystalline form, although it cannot be a structure with accurate bond lengths and bond angles. Other supporting characterization data {vide infra Materials and Methods) are consistent with the crystal structure. BORG-I contains three links per Zn4O secondary building unit. The structure is a non-interpenetrating cubic framework. To prove the correctness of the atomic positions in the framework the application of the SQUEEZE routine of A. Spek has been performed with the backbone framework only. However, atomic co-ordinates for the "non-SQUEEZE" structures are also presented. Final full matrix least-squares refinement on Fl converged to Rl = 0.0737 (F >2o(F)) and wRl = 0.2588 (all data) with GOF = 1.042. For the structure where the SQUEEZE program has not been employed, final full matrix least-squares refinement on Fl converged to Rl = 0.2884 (F >2σ(F)) and wRl = 0.6396 (all data) with GOF = 3.094. When only framework atoms were included in the latter structure factor calculation, the residual electron density in the F-map was located within the pores of BORG-I .

[00149] The empirical formula from the crystal structure refinement is C7 2 H36θi3Zn 4 (without any guest molecule), with a density of 0.123 g cm "3 . This model only contains the backbone of the framework. If all the atoms in the framework are considered, the calculated empirical formula is Ci3sHi38θ 43 Zn 4 , with a density of 0.246 g cm "3 .

[00150] Experimental Details for BORG-2 A light yellow cubic shape crystal (0.20 x 0.20 x 0.20 mm 3 ) of BORG-2 was placed in a 0.4 mm diameter borosilicate capillary along with a small amount of mother liquor. The capillary was flame sealed and mounted on a SMART APEXII three circle diffractometer equipped with a CCD area detector and operated at 1200 W power (40 kV, 30 mA) to generate Cu Ka radiation (λ = 1.5418 A) while being cooled to 258(2) K in a liquid N2 cooled stream of nitrogen. Data were

collected using the Bruker APEX2 software suite to carry out overlapping φ and ω scans at two different detector (2θ) settings (2θ = 28, 60°). 986 reflections with min. I/sigma 20 were harvested for unit cell determination from a total of 240 frames. The theta range for the unit cell determination is 2.350 to 37.375°. The bravis lattice of cubic F with a = 52.9482 A was chosen (FOM = 0.64).

[00151] The only optimal BORG-2 crystals suitable for analysis were generally small and weakly diffracting, and unfortunately, larger crystals, which might have improved the quality of the data, presented a lowered degree of crystallinity, and optimization of crystal growing conditions for large high-quality specimens has not yet been fruitful. Analysis of the data showed crystal decomposition during collection. Additionally, diffuse scattering from the highly disordered crown ethers and solvent in the void spaces within the crystal and from the capillary used mount the crystal contributes to the background noise and the 'washing out' of high angle data. A complete structure solution was not obtained due to the high Rint value (0.4205 before scale). Nevertheless, determination of the unit cell parameters was unambiguous. The unit cell constants and the space group information for BORG-2 was nearly identical to that of BORG-I . Thus, atom positions from BORG-I were used to model BORG-2. BORG-2 contains l ,5-dinaphthoparaphenylene-[36]crown-10 while BORG-I has bisparaphenylene-[34]-crown-10. This difference in the crown does not change the PXRD simulation pattern, since both BORG-I and BORG-2 are extremely disordered in the crown part of the structure. The structure of BORG-2 was characterized by powder X-ray diffraction.

[00152] Experimental and Simulated Powder X-Ray Diffraction Patterns.

Powder X-ray diffraction (PXRD) data were collected using a Bruker D8- Discover θ-2θ diffractometer in reflectance Bragg-Brentano geometry. Cu Ka radiation (λ = 1.5406 A; 1 ,600 W, 40 kV, 40 mA) was focused using a planar Gobel Mirror riding the Ka line. A 0.6 mm divergence slit was used for all measurements. Diffracted radiation was detected using a Vantec line detector (Bruker AXS) (6° 2θ sampling width) equipped with a Ni monochromator. All samples were mounted on a glass slide or a zero background quartz

plate fixed on a sample holder by dropping crystals and then leveling the sample surface with a wide blade spatula. The best counting statistics were achieved by using a 0.02° 2θ step scan from 2 - 50° with an exposure time of 0.4 s per step.

[00153] Thermal Gravimetric Analysis. All samples were run on a TA Instruments

Q-500 series thermal gravimetric analyzer with samples held in platinum pans in a continuous air flow atmosphere. Samples were heated at a constant rate of 5 °C/min during all TGA experiments.

[00154 ] The TGA trace of the MOF-1000 (Fig. 39) sample after being CHCI 3

(pentene stabilized) exchanged three days, three times each day and evacuated at room temperature for 12 h, is shown. The material is thermally stable to 330 0 C, and a sharp weight loss from that point onwards indicates the decomposition of the material. This weight-loss step from MOF-1000 to ZnO (77.7%) matches the calculated weight loss

(79.0%).

[00155] The TGA trace of the BORG-I (Fig. 40) sample after being Me 2 CO exchanged three days, three times each day, and evacuated at room temperature for 12 h, is shown in blue. The material is thermally stable to 300 0 C, and a sharp weight loss from that point onwards indicates the decomposition of the material. This weight-loss step from

BORG-I to ZnO (86.6%) matches the calculated weight loss (88.2%).

[00156] The TGA trace of the BORG-2 (Fig. 41) sample after being Me 2 CO exchanged three days, three times each day, and evacuated at room temperature for 12 h, is shown. The material is thermally stable to 300 0 C, and a sharp weight loss from that point onwards indicates the decomposition of the material. This weight-loss step from BORG-2 to

ZnO (85.0%) matches the calculated weight loss (88.8%).

[00157] A number of embodiments of the invention have been described.

Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.