Strategies, linkers and coordination polymers for high-performance sorbents
A linking ligand compound includes three bidentate chemical moieties distributed about a central chemical moiety. Another linking ligand compound includes a bidentate linking ligand and a monodentate chemical moiety. Coordination polymers include a plurality of metal clusters linked together by residues of the linking ligand compounds.
1. A coordination polymer defining a molecular framework, the coordination polymer comprising:
a plurality of metal atoms or metal clusters, and
a plurality of organic linking ligands, each linking ligand comprising a residue of a compound having Formula I or VII:
wherein:
R 1 and R 1′ are each independently CO 2 R 2 , CONR 2 2 , CN, a C 2-8 alkynyl, or a C 4-18 heteroatom-containing aromatic ring system;
R 2 is H, a metal cation, an organic cation, C 1-8 alkyl, C 1-8 perfluoroalkyl, a C 6-18 aromatic ring system, or a C 4-18 heteroatom-containing ring system;
A is a substituted or unsubstituted C 6-18 aromatic ring system or a C 4-18 heteroatom-containing ring system; and
B 1 , B 2 , B 3 are each independently a substituted or unsubstituted C 6-18 aromatic ring system, a C 4-18 heteroatom-containing ring system, C 7-18 alkyl aryl, or C 5-18 alkyl heteroaryl, wherein B 1 , B 2 , B 3 are distributed about the A moiety.
2. The coordination polymer of claim 1 further comprising at least one non-linking ligand.
3. The coordination polymer of claim 2 wherein the non-linking ligand is selected from the group consisting of O 2− , sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, sulfide, hydrogen sulphate, selenide, selenate, hydrogen selenate, telluride, tellurate, hydrogen tellurate, nitride, phosphide, arsenide, arsenate, hydrogen arsenate, dihydrogen arsenate, antimonide, antimonate, hydrogen antimonate, dihydrogen antimonate, fluoride, boride, borate, hydrogen borate, perchlorate, chlorite, hypochlorite, perbromate, bromite, hypobromite, periodate, iodite, hypoiodite, and combinations thereof.
4. The coordination polymer of claim 1 further comprising at least one adsorbed species.
5. The coordination polymer of claim 4 wherein the adsorbed species is selected from the group consisting of ammonia, carbon dioxide, carbon monoxide, hydrogen, amines, methane, oxygen, argon, nitrogen, argon, organic dyes, polycyclic organic molecules, and combinations thereof.
6. The coordination polymer of claim 1 wherein the metal clusters comprise a metal ion selected from the group consisting Group 1 through 16 metals of the IUPAC Periodic Table of the Elements including actinides, lanthanides and combinations thereof.
7. The coordination polymer of claim 1 wherein the metal cluster further contains at least one atom from the group consisting of N, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br, and I.
8. The coordination polymer of claim 1 having described by the following formula [(C 48 H 24 O 12 )Cu 3 .(solvent) n ] x where x is a real number and n is a number from 0 to 50.
9. The coordination polymer of claim 1 further comprising one or more guest molecules occupying space within the framework.
10. The coordination polymer of claim 9 wherein the guest molecules are selected from the group consisting of solvents, gases, amines, organic compounds, coordination compounds, polymers, organic particles, organometallic particles, inorganic particles, and combinations thereof.
11. The coordination polymer of claim 9 wherein the guest molecules are selected from the group consisting of water, small organic alkanes, arenes, ethers, haloalkanes, esters, amides, sulfides, sulfoxides, amines, ketones, aldehydes, alcohols, thiols, hydrogen, ammonia, methane, oxygen, nitrogen, argon, carbon monoxide, carbon dioxide, nitrous oxide, sulfur dioxide, sulfur trioxide, ethylene, acetylene, and combinations thereof.
12. The coordination polymer of claim 1 having formula [(C 15 H 7 O 6 ) 2 Cu 3 .(solvent) n ] x where x is a real number and n is a number from 0 to 50.
13. The coordination polymer of claim 1 wherein each linking ligand comprises a residue of a compound having formula VII:
14. The coordination polymer of claim 13 wherein R 1 and R 1′ are CO 2 H.
15. The coordination polymer of claim 13 wherein the center of mass of moiety B is at least 4 angstroms from the center of mass of moiety A.
16. The coordination polymer of claim 13 wherein the center of mass of moiety B is from about 7 to about 25 angstroms from the center of mass of moiety A.