Chemical framework compositions and methods of use
The disclosure provides metal organic frameworks useful for sensing, gas sorption, microelectronics and switches.
1. A metal organic framework comprising a linking moiety connecting at least two metals, the linking moiety having the structure:
wherein, FG refer to functional linking groups selected from the group consisting of 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 , that undergo condensation with a metal to link the at least two metals, wherein R is an alkyl group having from 1 to 5 carbon atoms, or an aryl group comprising 1 to 2 phenyl rings and wherein the functional linking group forms a coordination complex with the metals; and
wherein R 1 and R 4 are linked together to form a macrocycle and/or wherein R 2 and R 3 are linked together to form a macrocycle, wherein the macrocycle linking R 1 and R 4 and/or the macrocycle linking R 2 and R 3 each comprises seven or more ring atoms.
2. The metal organic framework of claim 1 , wherein the macrocycle is selected from the group consisting of a crown ether; and a cyclic macromolecule comprising C, O, N, or S.
3. The metal organic framework of claim 1 , wherein the macrocycle is selected from the group consisting of:
wherein the arrows denote R 1 and R 4 or R 2 and R 3 of the linking moiety.
4. The metal organic framework of claim 1 , wherein the linking moiety comprising the macrocycle or a functional group moiety with stereospecific and stereoelectronic control comprises a structure selected from the group consisting of structures I, XI-XV and XXVI-XXX or any combination thereof:
5. The metal organic framework of claim 1 , wherein the metal organic framework comprises a macrocycle selected from the group consisting of pseudorotaxane, rotaxane, catenane, chelates and cryptand.
6. The metal organic framework of claim 5 , wherein the catenane framework comprises linking moieties having a structure selected from the group consisting of structures XXXI-XXXIII:
7. The framework of claim 1 , wherein the functional linking group comprises a carboxylic acid functional group.
8. The framework of claim 1 , wherein the metal is a transition metal.
9. The framework of claim 1 , wherein the metal is 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.
10. A microelectronic switch comprising a metal organic framework of claim 1 .
11. The microelectronic switch of claim 10 , wherein at least two monodentate or multidentate cores are linked to one another by a structure selected from the group consisting of structures I, XI-XV, and XXVI-XXXIII and any combination thereof.
12. A sensor comprising a framework of claim 1 .
13. A gas separation device comprising a framework of claim 1 .
14. A small molecule separation/purification device comprising a framework of claim 1 .
15. A guest recognition device comprising a framework of claim 1 .
16. A chiral molecule separation medium comprising a framework of claim 1 .