# Patent

## Title
Porous crystalline materials, their synthesis and use

## Abstract

A porous crystalline material has a tetrahedral framework comprising a general structure, M1-IM-M2, wherein M1 comprises a metal having a first valency, wherein M2 comprises a metal having a second valency different from said first valency, and wherein IM is imidazolate or a substituted imidazolate linking moiety.

## Background
FIELD
This invention relates to porous crystallline materials, their synthesis and their use.
BACKGROUND
One known family of porous crystallline materials are the zeolitic materials, which are based on the 3-dimensional, four-connected framework structure defined by corner-sharing [TO4] tetrahedra, where T is any tetrahedrally coordinated cation. Among the known materials in this family are aluminosilicates that contain a three-dimensional microporous crystal framework structure of [SiO4] and [AlO4] corner sharing tetrahedral units, aluminophosphates that contain a three-dimensional microporous crystal framework structure of [AlO4] and [PO4] corner sharing tetrahedral units, and silicoaluminophosphates (SAPOs), in which the framework structure is composed of [SiO4], [AlO4] and [PO4] corner sharing tetrahedral units. Included in the zeolitic family of materials are over 180 different porous framework types, many of which have great commercial value as catalysts and adsorbents.
Recently a new family of porous materials has been synthesized that is based on [M(IM)4] tetrahedra in which IM is an imidazolate type linking moiety and M is a transition metal. These new materials are generally referred to as zeolitic imidazolate frameworks or ZIFs since the angle formed by imidazolates (IMs) when bridging transition metals is similar to the 145° angle of the Si—O—Si bond in zeolites. As a result, despite the infancy of this area of research, it has already been possible to synthesize ZIF counterparts of a large number of known zeolitic structures as well as produce porous framework types hitherto unknown to zeolites. Discussion of this research can be found in, for example, the following publications from Professor Yaghi and his co-workers: “Exceptional Chemical and Thermal Stability of Zeolitic Imadazolate Frameworks”, Proceedings of the National Academy of Sciences of U.S.A., Vol. 103, 2006, pages 10186-10191, “Zeolite A Imidazolate Frameworks”, Nature Materials, Vol. 6, 2007, pages 501 to 506, “High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture”, Science, Vol. 319, 2008, pages 939 to 943, “Colossal Cages in Zeolitic Imidazolate Frameworks as Selective Carbon Dioxide Reservoirs”, Nature, Vol. 453, 2008, pages 207 to 212, and “Crystals as Molecules: Postsynthesis Covalent Functionalization of Zeolitic Imidazolate Frameworks”, Journal of the American Chemical Society, Vol. 130, 2008, pages 12626 to 12627.
Much of this work on ZIF structures is summarized in U.S. Patent Application Publication No. 2007/0202038, the entire contents of which are incorporated herein by reference. In particular, the '038 application discloses a zeolitic framework, comprising the general structure: M-L-M, wherein M comprises a transition metal and L is a linking moiety comprising a structure selected from the group consisting of I, II, III, or any combination thereof:




wherein A1, A2, A3, A4, A5, A6, and A7 can be either C or N, wherein R5-R8 are present when A1 and A4 comprise C, wherein R1, R4 or R9 comprise a non-sterically hindering group that does not interfere with M, wherein R2, R3, R5, R6, R7, R8, R10, R11, and R12 are each individually an alkyl, halo-, cyano-, nitro-, wherein M1, M2, M3, M4, M5, and M6 each comprise a transition metal, wherein when the linking moiety comprises structure III, R10, R11, and R12 are each individually electron withdrawing groups. The '038 application also discloses that the zeolitic frameworks are useful as catalyst supports and as adsorbents for gases, particularly carbon dioxide.

In the zeolitic frameworks claimed in U.S. Patent Application Publication No. 2007/0202038, the metal species are all transition metals, typically tetrahedrally-coordinated divalent transition metals, especially Zn2+ and Co2+. The only example disclosed in U.S. Patent Application Publication No. 2007/0202038 that contains mixed-valence metals is ZIF-5, which has a non-porous framework comprising octahedrally-coordinated In3+ in addition to tetrahedrally-coordinated Zn2+.
In addition, a number of materials having framework structures comprising a metal cation and an anion which is either [B(IM)4]− or [Al(IM)4]− are known in the literature. However, most of these materials do not have a tetrahedral framework and/or appear to be non-porous structures.
For example, a cationic layered structure [PbB(IM)4](NO3) and its neutral iso-structure TIB(IM)4 were reported by Ziegler et al. in 2002 and 2004, respectively. See Ziegler et al. “Construction of a Functional Layered Solid Using Tetrakis(imidazolyl)borate Coordinating Anion”, Inorganic Chemistry, Vol. 41, 2002, pages 4984 to 4986 and Ziegler et al. “Lead and Thallium Tetrakis(imidazolyl)borates: Modifying Structure by Varying Metal and Anion”, Inorganic Chemistry, Vol. 43, 2004, pages 4272 to 4277. However, although Pb2+ and Tl+ in the aforementioned structures assume a coordination number of four, their coordination geometries severely deviate from tetrahedral. As a result the products reported by Ziegler et al. appear to be generally two-dimensional layered structures as distinct from zeolitic or zeolite-like open frameworks.
A compound formulated AgB(IM)4 was reported by Pettinari et al. in 2000 and a compound formulated CuB(IM)4 was reported by Pike et al. in 2005. See Pettinari et al. “Synthesis, Characterization and X-ray Structural Studies of Novel Dinuclear Silver(I) Complexes of Poly(azolyl)borate Ligands”, Inorganic Chimica Acta, Vol. 308, 2000, pages 65 to 72 and Pike et al. “Convenient Synthesis of Copper (I) Thiolates and Related Compounds”, Inorganic Chimica Acta, Vol. 358, 2005, pages 1331 to 1336. The silver and copper compounds were synthesized in methanol and water, respectively. Although the aforementioned formula are consistent with tetrahedral frameoworks, no information about the crystal structure or crystallinity of these two materials was reported. More importantly, the aforementioned formula were assigned to the as-synthesized materials based on elemental analyses. The fact that the two materials in their as-synthesized form do not contain guest species, e.g. solvent molecules, within the frameworks is a strong evidence of the materials being non-porous.
JP Patent Application Publication No. 2007087737 “Lithium Ion Conducting Material and Secondary Lithium Ion Battery Using It” discloses a series of lithium salts formulated Li+[M(Azo)4-n(Q)n]−, wherein M is either B or Al, wherein Azo is an azole residue or a substituted azole residue, wherein Q is a residue of a compound except for azoles, and wherein n is 0, 1, 2, 3. The preparative method for the lithium salts with n=0 is exemplified in the synthesis of LiAl(IM)4, wherein IM is imidazolate, and involves reacting LiAlH4 with imidazole. Elemental analysis of the as-synthesized material was reported to be consistent with the formula LiAl(IM)4. The fact that this material in the as-synthesized form does not contain guest species, e.g. solvent molecules, within the framework is a strong evidence of it being non-porous.
According to the present invention, a new series of porous crystalline materials has been synthesized which have a tetrahedral framework comprising a general structure, M1-IM-M2, wherein M1 comprises a metal having a first valency and particularly a monovalent metal selected from Li+, Cu+, and Ag+, wherein M2 comprises a metal having a second valency different from said first valency and particularly a trivalent element selected from B3+, Al3+, and Ga3+, and wherein IM is imidazolate or a substituted imidazolate linking moiety. Such materials offer new opportunities for catalytic applications since, for example, Cu+, Ag+, Al3+ and Ga3+ exhibit different chemical behaviour than the divalent transition metals typically used for ZIF synthesis. Moreover, by employing low atomic weight elements Li and B, rather than transition metals, it should be possible to produce adsorbents with improved gas uptake on a gravimetric basis.
SUMMARY
In one aspect, the invention resides in a porous crystalline material having a tetrahedral framework comprising a general structure, M1-IM-M2, wherein M1 comprises a metal having a first valency, wherein M2 comprises a metal having a second valency different from said first valency, and wherein IM is imidazolate or a substituted imidazolate linking moiety.
In one embodiment, M1 comprises a monovalent metal and M2 comprises a trivalent element.
Conveniently, M1 is a monovalent metal cation selected from Li+, Cu+, and Ag+, particularly Li+.
Conveniently, M2 is a trivalent element cation selected from B3+, Al3+, and Ga3+, particularly B3+.
Typically, the tetrahedral framework has a framework type selected from the group consisting of crb, dft, cag, sod, mer, rho, ana, lta, dia, zni, gme, lcs, frl, gis, poz and moz.
In a further aspect, the invention resides in a porous crystalline material having a tetrahedral framework comprising a structure selected from the group consisting of IV, V, VI, or any combination thereof:




wherein A1, A2, A3, A4, A5, A6, and A7 can be either C or N, wherein R5-R8 are present when A1 to A4 comprise C, wherein R1, R4 or R9 comprise a non-sterically hindering group that does not interfere with the adjacent M1 or M2, wherein R2, R3, R5, R6, R7, and R8 are each individually hydrogen, alkyl, halo, cyano, or nitro, wherein M1 comprises a monovalent metal cation, wherein M2 comprises a trivalent element cation, and wherein R10, R11, and R12 are each individually electron withdrawing groups.

In one embodiment, M1 is Li+, M2 is B3+, IM is IV, each of R1, R2 and R3 is hydrogen, the tetrahedral framework has the cag framework type, and the as-synthesized material contains guest species within the tetrahedral framework.
In yet a further aspect, the invention resides in a method of adsorbing a gas comprising contacting the gas with the porous crystalline material described herein.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an Oak Ridge Thermal Ellipsoid Plot (ORTEP) of Compound 1 of Example 1.
FIG. 2 illustrates the framework structure of ZIF-4 having the cag framework type.
FIG. 3 is an overlay of the powder X-ray diffraction pattern of the needle-shaped microcrystalline Compound 2 of Example 2, shown as a continuous trace, and the pattern calculated from the structure of the large crystals of Compound 2 of Example 2, shown as a stick pattern.



DETAILED DESCRIPTION OF THE EMBODIMENTS
Disclosed herein is a new family of porous crystalline materials having a tetrahedral framework comprising a general structure, M1-IM-M2, wherein M1 comprises a metal having a first valency, wherein M2 comprises a metal having a second valency different from said first valency, and wherein IM is imidazolate or a substituted imidazolate linking moiety. Also disclosed herein is a process for synthesizing the new family of materials and a method of using the materials to adsorb gases, such as carbon dioxide.
Typically, M1, is a monovalent metal cation, such as Li+, Na+, K+, Cs+, Rb+, Cu+, Ag+ and Au+. More particularly, M1 is a monovalent metal cation selected from Li+, Cu+, and Ag+, particularly Li+.
Typically, M2 is a trivalent element cation, such as B3+, Al3+, Ga3+, In3+, Fe3+, Cr3+, Sc3+, Y3+, and La3+ wherein La is any lanthanide metal. More particularly, M1 is a trivalent element cation selected from B3+, Al3+, or Ga3+, particularly B3+.
Generally, the porous crystalline materials described herein have a tetrahedral framework comprising a structure selected from the group consisting of IV, V, VI, or any combination thereof:




wherein A1, A2, A3, A4, A5, A6, and A7 can be either C or N, wherein R5-R8 are present when their respective A1 to A4 comprise C, wherein R1, R4 or R9 comprise a non-sterically hindering group that does not interfere with the adjacent M1 or M2, wherein R2, R3, R5, R6, R7, and R8 are each individually hydrogen, alkyl, halo, cyano, or nitro, wherein M1 comprises a monovalent metal cation, wherein M2 comprises a trivalent element cation, and wherein, if present, R10, R11, and R12 are each individually electron withdrawing groups.

In one embodiment, each of R1, R4 and R9 is independently selected from hydrogen, methyl, ethyl, nitro, formyl, halo, and cyano groups.
Suitable electron withdrawing groups for each of R10, R11, and R12 include nitro, cyano, fluoro and chloro groups.
Examples of family members of the novel porous crystalline materials described herein comprise structures selected from the group consisting of VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, and XVIII:







These imidazolate linking moieties have also been successfully used in the syntheses of ZIFs, as reported by Professor Yaghi and his co-workers in the following publications: “Exceptional Chemical and Thermal Stability of Zeolitic Imadazolate Frameworks”, Proceedings of the National Academy of Sciences of U.S.A., Vol. 103, 2006, pages 10186-10191, “Zeolite A Imidazolate Frameworks”, Nature Materials, Vol. 6, 2007, pages 501 to 506, “High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture”, Science, Vol. 319, 2008, pages 939 to 943, “Colossal Cages in Zeolitic Imidazolate Frameworks as Selective Carbon Dioxide Reservoirs”, Nature, Vol. 453, 2008, pages 207 to 212, and “Crystals as Molecules: Postsynthesis Covalent Functionalization of Zeolitic Imidazolate Frameworks”, Journal of the American Chemical Society, Vol. 130, 2008, pages 12626 to 12627.
The new family of porous crystalline materials disclosed herein can have tetrahedral framework structures of any type. The framework type of a porous crystalline material is denoted herein by a mnemonic code consisting of three bold-face lower-case letters. This system of symbols was introduced by Professors O'Keeffe and Yaghi, and adopted in the research on ZIFs. General information about the symbol system can be found, for example, in the publication by O'Keeffe and Yaghi et al. “Reticular Chemistry: Ocurrence and Taxonomy of Nets and Grammar for the Design of Frameworks”, Accounts of Chemical Research, Vol. 38, 2005, pages 176 to 182, and at the Reticular Chemistry Structure Resource (RCSR) website http://rcsr.anu.edu.au/home. We note that the concepts “framework type”, “topology” and “net” are used essentially interchangeably in the chemical literature. These mnemonic codes should not be confused or equated with actual materials.
Typically, a porous crystalline material of the present invention is iso-structural to a known ZIF, and assumes a tetrahedral framework type selected from the group consisting of crb, dft, cag, sod, mer, rho, ana, lta, dia, zni, gme, lcs, frl, gis, poz and moz. All of these framework types have been realized in the syntheses of ZIFs.
In one embodiment, the monovalent metal, M1, is Li+, the trivalent element, M2, is B3+, IM is imidazolate linking moiety, i.e. structure VII, and the tetrahedral framework has the cag framework type. The as-synthesized material contains guest species within the framework.
Synthesis of the present porous crystalline material is based on a reaction of [M1(L)n]Xx and Aa[M2(IM)4],

    wherein M1, M2 and IM are the same as described above,
    L is a neutral ligand, typically ammonia, an amine, phosphine, nitrile, or ether;
    n is a non-negative integer ranging from 0 to 12;
    X is an anion, typically a halide, nitrate, perchlorate, acetate, trifluoromethanesulfonate, or acetylacetonate;
    A is a cation, typically Na+, K+, tetraalkylammonium [NR4]+, or tetraalkylphosponium [PR4]+; and
    x and a are each a non-negative integer.


The reaction takes place in a polar aprotic solvent and, in some cases, in the presence of a template. The polar aprotic organic solvent is typically an amide (e.g. N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethylpropyleneurea), a sulfoxide (e.g. dimethylsulfoxide), or a phosphoramide (e.g. hexamethylphosphoramide). If present, the template is typically a neutral organic compound, such as an ether, ketone, ester, amine, nitrile, nitro compound, phosphine, hydrocarbon, or halide.
Typically the synthesis procedure involves mixing a solution of [M1(L)n]Xx and a solution of Aa[M2(IM)4], both in a polar aprotic organic solvent, at a temperature of about −78° C. (dry-ice bath temperature) to about 153° C. (the normal boiling point of N,N-dimethylformamide), and allowing the materials to react at this temperature for about 0.5 hour to about 72 hours. The molar ratio of [M1(L)n]Xx to Aa[M2(IM)4] is in the range from about 0.1 to about 10. If the by-product AX precipitates, the solid and the solution are separated. Optionally, a template compound is added to the solution at this point. The quantity of the template compound is in such a range that, at the lower limit, it is equimolar to one of the two reactants that is smaller in molar quantity, and at the upper limit, it is equimolar to the solvent. The solution is kept at a temperature of about −78° C. to about 153° C. to allow the product to crystallize. When the crystallization step is completed, normally in about 0.5 hour to about 168 hours, the resultant porous crystalline material is recovered.
Li+, Cu+, Ag+ are particularly effective in displacing the cation A (Na+, K+, NR4+, PR4+) of the reactant Aa[M2(IM)4] because they all form significantly stronger bonds with the IM linking moiety than A. Li+, Cu+, Ag+ are all effective in the crystallization of the present porous crystalline materials because they all prefer tetrahedral coordination.
The reactants Aa[M2(IM)4] used in the syntheses of the present porous crystalline materials are prepared beforehand. The preparation is particularly convenient when M2=B3+, Al3+, Ga3+. The preparative procedures for the boron compound can be found in, for example, Moore et al. “Studies In The Tetraarylborates, Part VII. The Preparation and Reagent Properties of Some New Nitrogen Heterocyclic Tetraarylborates—Especially Sodium Tetrakis(1-Imidazolyl)borate, A Novel Gravimetric Reagent for Hydrogen Ion”, Analytica Chimica Acta, Vol. 100, 1978, pages 457 to 467, and Ziegler et al. “Lead and Thallium Tetrakis(imidazolyl)borates: Modifying Structure by Varying Metal and Anion”, Inorganic Chemistry, Vol. 43, 2004, pages 4272 to 4277. These preparations all involve a reaction between BH4− and H-IM, wherein H-IM is imidazole or a substituted imidazole. This chemistry is applicable to Al3+ and Ga3+ because Al and Ga exhibit chemical properties similar to B and because the AlH4− and GaH4− compounds are readily available.
The present porous crystalline materials in the as-synthesized form contain guest species, typically solvent and/or template molecules, within the tetrahedral frameworks. The guest species can be removed either by evacuation at a pressure less than 50 mTorr at a temperature of about 70° C. to about 300° C., or by exchange with an organic solvent of small molecular size, e.g. acetonitrile, followed by the evacuation process described above. The removal of guest species results in internal pore volume that can be used to adsorb various gases, such as carbon dioxide, carbon monoxide, hydrocarbons, hydrogen, nitrogen, oxygen, noble gases and amines.
The size and shape of the pores in the present crystalline materials can be controlled by the choice of imidazolate linking moiety, solvent and template. As a result, the present porous crystalline materials show significant potential for use as catalysts and in the storage and separation of gases.
From the viewpoint of catalysis, the incorporation of Cu+, Ag+, Al3+, and Ga3+ will enable unique catalytic chemistry that is unavailable to the metals used thus far for ZIFs, typically divalent transition metals, such as Zn2+, Co2+.
In the area of gas storage and separation, which is currently the most important application of ZIFs, the use of very light metals, such as Li and B, is highly desirable for improving gas uptake on a gravimetric basis. For example, a porous material with chemical composition LiB(IM)4 is expected to show 39% higher uptake in the unit of mmole/g than the iso-structural Zn(IM)2 material (the formula weights of Li0.5B0.5(IM)2 and Zn(IM)2 are 143 and 199, respectively; here IM is imidazolate).
The invention will now be more particularly described with reference to the Examples and the accompanying drawings.
EXAMPLE 1
A solution of 14 mg lithium chloride (LiCl, 0.33 mmole) in 5 mL N,N-dimethylformamide (DMF) was added to a solution of 100 mg sodium tetrakis(1-imidazolyl)borate (NaB(IM)4, 0.33 mmole) in 5 mL DMF in a 20-mL glass vial. When the precipitation of sodium chloride completed (typically in about 2 hrs), the clear solution was transferred to another 20-mL glass vial, and mixed with 5 mL tetrahydrofuran (THF). Polyhedral crystals appeared shortly on the glass wall and were allowed to grow over a period of about 8 hrs. The mother liquor was then removed and the crystals were washed thoroughly with THF and dried in vacuo. 35 mg of highly crystalline product LiB(IM)4.Guest (Compound 1) was obtained (30% yield; Guest is a mixture of THF and DMF).
A colorless polyhedron-shaped crystal of Compound 1 with approximate dimensions 0.08×0.19×0.21 mm, was used for X-ray crystallographic analysis. The X-ray intensity data were measured at 133(2) K, cooled by Rigaku-MSC X-Stream 2000, on a Bruker SMART APEX CCD area detector system equipped with a graphite monochromator and a MoKα fine-focus sealed tube (α=0.71073 Å) operated at 1600 watts power (50 kV, 32 mA). The detector was placed at a distance of 5.8 cm from the crystal.
A total of 1515 frames were collected with a scan width of 0.3° in ω and an exposure time of 20 seconds/frame. The total data collection time was about 11 hours. The frames were integrated with the Bruker SAINT software package using a narrow-frame integration algorithm. The integration of the data using a Orthorhombic unit cell yielded a total of 27071 reflections to a maximum θ angle of 28.40° (0.90 Å resolution), of which 4692 were independent, completeness=98.3%, Rint=0.0759, Rsig=0.0611 and 3273 were greater than 2σ (I). The final cell constants: a=14.382(5) Å, b=14.809(5) Å, c=17.869(6) Å, α=90°, β=90°, γ=90°, volume=3806(2) Å3, were based upon the refinement of the XYZ-centroids of 2336 reflections above 20σ (I) with 2.278°<θ<23.570°. Analysis of the data showed negligible decay during data collection. Data were corrected for absorption effects using the multi-scan technique (SADABS). The ratio of minimum to maximum apparent transmission was 0.5697.
The structure was solved and refined using the Bruker SHELXTL (Version 6.1) Software Package, using the space group Pbca with Z=8 for the formula unit Li B C16 H20 N8 O, i.e., LiB(IM)4.THF. The five non-hydrogen atoms of the THF molecule were clearly revealed in difference Fourier maps. However, refinement of these atoms was unsuccessful due to a slight disorder of the THF molecule that was not easy to model accurately. The disorder was caused by the superimposition of THF and DMF, which were respectively the major and minor components of the guest mixture. In order to improve the refinement of the light atoms on the framework, PLATON/SQUEEZE routine was used to remove the electron density of the disordered guest molecules. Final anisotropic full-matrix least-squares refinement on F2 with 199 variables converged at R1=7.24% for the observed data and wR2=17.77% for all data. The goodness-of-fit was 1.041. The largest peak on the final difference map was 0.289 e−/Å3 and the largest hole was −0.267 e−/Å3. Based on the final model, the calculated density of the crystal is 0.998 g/cm3 and F(000) amounts to 1184 electrons.
The validity of this structure is supported by the R factors, goodness-of-fit and residual electron densities described above and by very reasonable displacement parameters of the framework atoms listed in Table 1. In addition, the treatment of the guest portion of the structure is validated by the results of PLATON/SQUEEZE shown in Table 2. The routine has identified eight cavities per unit cell. Each has a volume of 146 to 148 Å3 and contains 38 electrons. Both the volume and the electron count support the assignment of one guest molecule per cavity (both THF and DMF have 5 non-hydrogen atoms and 40 electrons per molecule), and therefore the formula of the crystal LiB(IM)4.Guest.







TABLE 1







Atomic coordinates and equivalent isotropic atomic displacement


parameters (Å2) for Compound 1


U(eq) is defined as one third of the trace of the orthogonalized


Uij tensor.












x
y
z
U(eq)














N1
0.91688(12)
0.16097(12)
0.62417(9)
0.0176(4)


N4
1.14471(13)
−0.01735(13)
0.64484(11)
0.0277(5)


N7
0.95613(12)
0.19942(12)
0.75802(9)
0.0182(4)


N5
1.05049(11)
0.26554(12)
0.64962(9)
0.0172(4)


N2
0.84096(13)
0.13435(14)
0.51725(10)
0.0256(4)


N3
1.06254(12)
0.10166(12)
0.68310(9)
0.0173(4)


N6
1.17178(13)
0.35073(13)
0.61547(11)
0.0239(4)


N8
0.88028(13)
0.26633(14)
0.85190(10)
0.0259(4)


C9
1.14427(14)
0.27288(15)
0.64364(12)
0.0208(5)


C6
1.07483(15)
0.03737(15)
0.63057(12)
0.0218(5)


C12
0.92037(15)
0.27681(15)
0.78558(12)
0.0223(5)


B1
0.99664(16)
0.18318(16)
0.67886(13)
0.0173(5)


C7
1.01622(16)
0.34659(15)
0.62324(13)
0.0234(5)


C3
0.91335(15)
0.17280(15)
0.54931(12)
0.0217(5)


C10
0.93655(17)
0.13448(16)
0.81107(13)
0.0282(5)


C8
1.09050(16)
0.39694(16)
0.60277(13)
0.0256(5)


C1
0.83986(17)
0.10941(18)
0.64045(14)
0.0335(6)


C2
0.79516(18)
0.0938(2)
0.57474(14)
0.0368(6)


C5
1.18061(16)
0.01327(16)
0.71150(14)
0.0287(5)


C11
0.89095(17)
0.17620(16)
0.86780(13)
0.0299(6)


C4
1.13132(16)
0.08573(15)
0.73551(13)
0.0247(5)


Li1
0.8107(3)
0.1311(2)
0.4063(2)
0.0207(8)
















TABLE 2







Location and volume of and number of electrons within the


cavities in the unit cell of Compound 1











Coordinates





of Centroid
Volume
Electron














Cavity
X
Y
Z
(Å3)
(e−)







1
0.341
0.305
0.401
147
38



2
0.841
0.305
0.099
147
38



3
0.341
0.194
0.901
148
38



4
0.841
0.194
0.599
148
38



5
0.159
0.805
0.401
146
38



6
0.659
0.805
0.099
146
38



7
0.159
0.694
0.901
146
38



8
0.659
0.694
0.599
146
38










Compound 1 has a tetrahedral framework of mixed-valence metal imidazolate, M1M2(IM)4, wherein M1 and M2 are monovalent and trivalent element cations, respectively. This is clearly depicted in an Oak Ridge Thermal Ellipsoid Plot (ORTEP) of Compound 1, showing two adjacent metal cations, Li+ and B3+, both tetrahedrally coordinated by four imidazolate linkers (FIG. 1). The lengths of Li—N and B—N bonds all fall in the ranges well established in the literature (Table 3), confirming the correct assignment of the identity of the metals. The tetrahedral coordination geometry of each metal cation is near perfect, evidenced by N—Li—N and N—B—N bond angles, all of which are very close to the ideal tetrahedral angle of 109.5° (Table 3). For comparison, Table 3 also lists N—Tl—N and N—B—N bond angles observed in the single-crystal structure of the two-dimensional layered compound TlB(IM)4 disclosed by Ziegler et al. in “Lead and Thallium Tetrakis(imidazolyl)borates: Modifying Structure by Varying Metal and Anion”, Inorganic Chemistry, Vol. 43, 2004, pages 4272 to 4277. The non-tetrahedral coordination of Tl+ discourages the formation of zeolitic or zeolite-like open frameworks, whereas the tetrahedral coordination of Li+ facilitates such.







TABLE 3







Bond lengths and angles involving Li+ or B3+ observed in the


crystal structure of Compound 1 and bond angles involving Tl+ or B3+


observed in the crystal structure of the layered compound TlB(IM)4









Bond lengths of
Bond angles of
Bond angles of


Compound 1 (Å)
Compound 1 (°)
TlB(IM)4 (°)












Li—N
B—N
N—Li—N
N—B—N
N—Tl—N
N—B—N















2.021
1.536
104.289
108.000
77.093
107.774


2.030
1.537
106.639
108.808
78.757
107.824


2.053
1.542
109.412
109.191
78.899
109.180


2.062
1.549
109.802
109.240
89.721
110.183




112.985
109.393
92.251
110.381




113.159
112.148
155.030
111.501









The framework type of Compound 1 is the same as ZIF-4, which in turn is the same as that of mineral Calcium Gallate (denoted cag hereafter). Although the cag framework type is not a zeolitic framework type, it is a three-dimensional tetrahedral framework, and when adopted by a ZIF, it imparts the material internal cavities and 6-ring channels that can be accessible (FIG. 2). Table 4 compares the unit cell parameters of Compound 1 with those of ZIF-4 reported by Yaghi et al. in “Exceptional Chemical and Thermal Stability of Zeolitic Imadazolate Frameworks”, Proceedings of the National Academy of Sciences of U.S.A., Vol. 103, 2006, pages 10186-10191. They are identical except the slight contraction of Compound 1 in cell edges, which is expected based on typical bond lengths of Li—N, B—N and Zn—N. Therefore, the synthesis of Compound 1 demonstrates the concept of substituting divalent metal in a neutral tetrahedral framework of ZIF with alternating monovalent and trivalent elements while preserving the framework type.







TABLE 4







Comparison of the compositions and unit cell parameters


of Compound 1 and ZIF-4.










Framework
Unit cell parameters












Material
composition
Space group
a (Å)
b (Å)
c (Å)





ZIF-4
Zn(IM)2
Pbca,
15.395 (2)
15.307 (2)
18.426




orthorhombic


(2)  


Com-
LiB(IM)4
Pbca,
14.382 (5)
14.809 (5)
17.869


pound 1

orthorhombic


(6)  









EXAMPLE 2
To demonstrate the templating effect of THF in the synthesis of Compound 1, Example 1 was repeated without the addition of THF and produced a needle-shaped microcrystalline product LiB(IM)4 (Compound 2). Large crystals of Compound 2 suitable for single-crystal X-ray diffraction were obtained from an alternative route, which is a very slow transformation from Compound 1 to Compound 2 in THF under ambient conditions. The crystal transformation process likely involves trace amount of water present in THF, and typically occurs to an appreciable extent in about one month. The needle-shaped microcrystalline product and the large crystals are the same crystalline phase, evidenced by the excellent agreement of the powder X-ray diffraction pattern of the former and the pattern calculated from the crystal structure of the latter (FIG. 3).
The crystal structure of Compound 2 was successfully solved and refined (Tables 5 and 6). The LiB(IM)4 tetrahedral framework of Compound 2 is non-porous, and consequently does not contain guest species. This is evidenced by the very low residual electron densities of the final converged refinement of a structural model without any guest species (Table 5). The observed bond lengths are consistent with the typical values for Li—N and B—N bonds, and the observed bond angles confirm the tetrahedral coordination geometry of each T atom (Table 7). As far as framework type is concerned, Compound 2 is the mixed-valence counterpart of ZIF-61 with the zni framework type reported by Yaghi et al. in “High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture”, Science, Vol. 319, 2008, pages 939 to 943 (Table 8). In comparison to ZIF-61, Compound 2 shows a slight contraction in cell edges due to the difference in bond lengths (Zn—N versus Li—N and B—N) and a slight lowering in space-group symmetry due to the replacement of the only unique T site (Zn2+) with two alternating T sites (Li+ and B3+).







TABLE 5





Crystal data and structure refinement for Compound 2


















Empirical formula
C12H12BLiN8 [i.e., LiB(IM)4]



Formula weight
286.05



Temperature
100(2) K



Wavelength
0.71073 Å



Crystal system, space group
Tetragonal, I41cd











Unit cell dimensions
a = 22.4981(7) Å
α = 90°




b = 22.4981(7) Å
β = 90°




c = 11.5015(6) Å
γ = 90°










Volume
5821.7(4) Å3



Z, Calculated density
16, 1.305 g/cm3



Absorption coefficient
0.086 mm−1



F(000)
2368



Crystal size
0.13 × 0.02 × 0.02 mm



Theta range for data collection
1.81° to 28.28°.



Limiting indices
−29 ≦ h ≦ 29, −29 ≦ k ≦ 29,




−14 ≦ l ≦ 14



Reflections collected/unique
80347/3505 [R(int) = 0.1380]



Completeness to theta = 28.28
98.3%



Refinement method
Full-matrix least-squares on F2



Data/restraints/parameters
3505/1/199



Goodness-of-fit on F2
0.969



Final R indices [I > 2σ(I)]
R1 = 0.0345, wR2 = 0.0766



R indices (all data)
R1 = 0.0493, wR2 = 0.0827



Largest diff. peak and hole
0.204 and −0.200 e−/Å3

















TABLE 6







Atomic coordinates (×104) and equivalent isotropic displacement


parameters (Å2 × 103) for Compound 2


U(eq) is defined as one third of the trace of the orthogonalized


Uij tensor.












x
y
z
U(eq)

















B(1)
1485(1)
 983(1)
3244(1)
12(1)



C(1)
2494(1)
 918(1)
4386(1)
15(1)



C(2)
1958(1)
1701(1)
4775(1)
16(1)



C(3)
2471(1)
1719(1)
5396(1)
16(1)



C(4)
1396(1)
1130(1)
 999(1)
15(1)



C(5)
1606(1)
1940(1)
1959(2)
18(1)



C(6)
1510(1)
2068(1)
 817(1)
20(1)



C(7)
 374(1)
1311(1)
3253(1)
16(1)



C(8)
 694(1)
 973(1)
4918(1)
19(1)



C(9)
 100(1)
1091(1)
4981(1)
22(1)



C(10)
1162(1)
−128(1)
3285(1)
15(1)



C(11)
1970(1)
 37(1)
2293(1)
16(1)



C(12)
1826(1)
−549(1)
2240(1)
18(1)



Li(1)
3556(1)
1000(1)
6061(2)
16(1)



N(1)
1969(1)
1185(1)
4119(1)
13(1)



N(2)
2812(1)
1221(1)
5154(1)
16(1)



N(3)
1534(1)
1331(1)
2087(1)
13(1)



N(4)
1375(1)
1555(1)
 210(1)
17(1)



N(5)
 873(1)
1113(1)
3800(1)
13(1)



N(6)
−104(1)
1308(1)
3929(1)
20(1)



N(7)
1540(1)
 314(1)
2969(1)
13(1)



N(8)
1315(1)
−656(1)
2876(1)
18(1)

















TABLE 7







Bond lengths and angles involving Li+ or B3+ observed in the


crystal structure of Compound 2












Bond lengths






of Compound 2

Bond angles of



(Å)

Compound 2 (°)












Li—N
B—N
N—Li—N
N—B—N







2.034
1.544
102.948
107.606



2.065
1.547
105.536
108.089



2.083
1.547
106.496
108.896



2.091
1.551
108.060
109.950





115.254
111.123





117.511
111.156

















TABLE 8







Comparison of the compositions and unit cell parameters


of Compound 2 and ZIF-61









Unit cell parameters













Framework
Space





Material
composition
group
a (Å)
b (Å)
c (Å)





ZIF-61
Zn(IM)2
I41/acd,
23.4803 (3)
23.4803 (3)
12.5545




Tetragonal


(3)   


Com-
LiB(IM)4
I41cd,
22.4981 (7)
22.4981 (7)
11.5015


pound 2

Tetragonal


(6)   









While the present invention has been described and illustrated by reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to variations not necessarily illustrated herein. For this reason, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.

## Claims

1. A porous crystalline material having a tetrahedral framework comprising a general structure, M1-IM-M2, wherein M1 comprises a metal having a first valency, wherein M2 comprises a metal having a second valency different from said first valency, and wherein IM is imidazolate or a substituted imidazolate linking moiety, and wherein one or more of the following is satisfied: M1 comprises a monovalent metal and M2 comprises a trivalent element; M1 is Li+; and M2 is B3+.

2. The porous crystalline material of claim 1 wherein M1 comprises a monovalent metal and M2 comprises a trivalent element.

3. The porous crystalline material of claim 1 wherein M1 is a monovalent metal cation selected from Li+, Na+, K+, Cs+, Rb+, Cu+, Ag+, or Au+.

4. The porous crystalline material of claim 1 wherein M1 is a monovalent metal cation selected from Li+, Cu+, or Ag+.

5. The porous crystalline material of claim 1 wherein M1 is Li+.

6. The porous crystalline material of claim 1 wherein M2 is a trivalent element cation selected from B3+, Al3+, Ga3+, In3+, Fe3+, Cr3+, Sc3+, Y3+, or La3+ wherein La is any lanthanide metal.

7. The porous crystalline material of claim 1 wherein M2 is a trivalent element cation selected from B3+, Al3+, or Ga3+.

8. The porous crystalline material of claim 1 wherein M2 is B3+.

9. The porous crystalline material of claim 1 wherein the tetrahedral framework has a framework type selected from the group consisting of crb, dft, cag, sod, mer, rho, ana, lta, dia, zni, gme, lcs, frl, gis, poz and moz.

10. The porous crystalline material of claim 1 wherein IM is an unsubstituted imidazolate group.

11. A porous crystalline material having a tetrahedral framework comprising a structure selected from the group consisting of IV, V, VI, or any combination thereof:



wherein A1, A2, A3, A4, A5, A6, and A7 can be either C or N, wherein R5-R8 are present when A1 to A4 comprise C, wherein R1, R4 or R9 comprise a non-sterically hindering group that does not interfere with the adjacent M1 or M2, wherein R2, R3, R5, R6, R7, and R8 are each individually hydrogen, alkyl, halo, cyano, or nitro, wherein M1 comprises a monovalent metal cation, wherein M2 comprises a trivalent element cation, and wherein R10, R11, and R12 are each individually electron withdrawing groups.

12. The porous crystalline material of claim 11 wherein M1 is a monovalent metal cation selected from Li+, Na+, K+, Cs+, Rb+, Cu+, Ag+, or Au+.

13. The porous crystalline material of claim 11 wherein M1 is a monovalent metal cation selected from Li+, Cu+, or Ag+.

14. The porous crystalline material of claim 11 wherein M1 is Li+.

15. The porous crystalline material of claim 11 wherein M2 is a trivalent element cation selected from B3+, Al3+, Ga3+, In3+, Fe3+, Cr3+, Sc3+, Y3+, or La3+ wherein La is any lanthanide metal.

16. The porous crystalline material of claim 11 wherein M2 is a trivalent element cation selected from B3+, Al3+, or Ga3+.

17. The porous crystalline material of claim 11 wherein M2 is B3+.

18. The porous crystalline material of claim 11 wherein the tetrahedral framework has a framework type selected from the group consisting of crb, dft, cag, sod, mer, rho, ana, lta, dia, zni, gme, lcs, frl, gis, poz and moz.

19. The porous crystalline material of claim 11 and comprising a structure selected from the group consisting of VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, and XVIII:

20. The porous crystalline material of claim 19 having structure VII wherein M1 is Li+, M2 is B3+, the tetrahedral framework has the cag framework type, and the as-synthesized material contains guest species within the tetrahedral framework.

21. A method of adsorbing a gas comprising contacting the gas with the porous crystalline material of claim 1.

22. The method of claim 21 wherein the gas is hydrogen, nitrogen, oxygen, a noble gas, carbon monoxide, carbon dioxide, a hydrocarbon or an amine.

23. A method of separating a gas from a fluid stream containing the gas comprising contacting the fluid stream with the porous crystalline material of claim 1.

24. The method of claim 23 wherein the gas is hydrogen, nitrogen, oxygen, a noble gas, carbon monoxide, carbon dioxide, a hydrocarbon or an amine.

25. A method of adsorbing a gas comprising contacting the gas with the porous crystalline material of claim 11.

26. The method of claim 21 wherein the gas is hydrogen, nitrogen, oxygen, a noble gas, carbon monoxide, carbon dioxide, a hydrocarbon or an amine.

27. A method of separating a gas from a fluid stream containing the gas comprising contacting the fluid stream with the porous crystalline material of claim 11.

28. The method of claim 24 wherein the gas is hydrogen, nitrogen, oxygen, a noble gas, carbon monoxide, carbon dioxide, a hydrocarbon or an amine.