Metal-organic framework materials based on icosahedral boranes and carboranes

1. A metal-organic framework (MOF) comprising a polymeric crystalline structure of Zn 3 (OH)(p-CDC) 2.5 L m , wherein p-CDC is 1,12-dihydroxycarbonyl-1,12-dicarba-closo-dodecaborane, L is a solvent, and m is an integer from 0 to 4.

2. The MOF of claim 1 , wherein m is different from 0 and at least one L is diethylformamide.

3. The MOF of claim 2 , wherein m is different from 0 or 1 and each L is diethylformamide.

4. The MOF of claim 1 , wherein m is 2.

5. The MOF of claim 1 , wherein m is 4.

6. The MOF of claim 1 having a pore size of about 4 to about 11 Å.

7. The MOF of claim 6 , wherein the pore size is about 4.5 to about 9.5 Å.

8. The MOF of claim 1 having a hydrogen gas uptake of about 0.5 wt % to about 2.4 wt % at 77 K and 1 atm.

9. The MOF of claim 8 , wherein the H 2 uptake is about 1.3 wt % to about 2.1 wt %.

10. A composition comprising the MOF of claim 1 and one or more of a binder, an organic viscosity-enhancing compound, and a liquid.

11. The composition of claim 10 , wherein the binder is selected from the group consisting of silica, an oxide of magnesium, an oxide of beryllium, a clay, and mixtures thereof.

12. The composition of claim 10 , wherein the organic viscosity-enhancing compound is selected from the group consisting of cellulose, starch, polyacrylate, polymethacrylate, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene, polytetrahydrofuran, and mixtures thereof.

13. The composition of claim 10 , wherein the liquid is selected from the group consisting of water, methanol, ethanol, propanol, n-butanol, isobutanol, tert-butanol, and mixtures thereof.

14. A method of storing a gas comprising exposing a gas to a MOF of claim 1 under conditions sufficient for the MOF to uptake the gas.

15. The method of claim 14 , wherein the MOF uptakes the gas at about 0.5 wt % to about 2.5 wt % at 77 K and 1 atm.

16. The method of claim 14 , wherein the gas is hydrogen.

17. A metal-organic framework (MOF) comprising a polymeric crystalline structure of a metal and a carborane ligand or an icosohedral borane ligand, and optionally a solvent.

18. The MOF of claim 17 substantially free of a solvent.

19. The MOF of claim 17 , wherein the metal is selected from the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Zr 4+ , Hf 4+ , V 4+ , V 3+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Mn 2+ , Re 3+ , Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Rh 2+ , Rh + , Ir 2+ Ir + , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , Au + , Zn 2+ , Cd 2+ , Hg 2+ , Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Si 4+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As + , Sb 5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ , Bi + , and mixtures thereof.

20. The MOF of claim 17 , wherein the carborane ligand is selected from the group consisting of

and

mixtures thereof,

wherein M is selected from the group consisting of nickel, copper, cobalt, iron, and zinc.

21. The MOF of claim 17 , wherein the metal comprises zinc, nickel, cobalt, manganese, or a mixture thereof.

22. The MOF of claim 17 , wherein the carborane ligand comprises

and the metal comprises zinc.

23. The MOF of claim 22 comprising Zn 2 (BCPD) 2 L m , wherein L is a solvent and m is an integer from 0 to 4.

24. The MOF of claim 17 , wherein the carborane ligand comprises

and the metal comprises zinc.

25. The MOF of claim 24 comprising Zn 3 (OH)(p-bis-CDC) 2.5 L m , wherein L is a solvent and m is an integer from 0 to 4.

26. The MOF of claim 17 , wherein the carborane ligand comprises

and the metal comprises cobalt.

27. The MOF of claim 26 comprising Co 4 (OH 2 )(p-CDC) 3 L m , wherein L is a solvent and m is an integer from 0 to 4.

28. The MOF of claim 17 , wherein the carborane ligand comprises

and the metal comprises manganese.

29. The MOF of claim 28 comprising Mn(p-CDC)L m , wherein L is a solvent and m is an integer from 0 to 4.

30. The MOF of claim 17 having a surface area of about 100 to about 4000 m 2 /g.

31. The MOF of claim 30 having a surface area of about 150 to about 1500 m 2 /g.

32. A method of storing a gas comprising exposing the gas to the MOF of claim 17 under conditions sufficient for the MOF to uptake the gas.