Linker-directed vertex desymmetrization for the production of coordination polymers with high porosity.
Five non-interpenetrated microporous coordination polymers (MCPs) are derived by vertex desymmetrization using linkers with symmetry inequivalent coordinating groups, and these MCPs include properties such as rare metal clusters, new network topologies, and supramolecular isomerism. Gas sorption in polymorphic frameworks, UMCM-152 and UMCM-153 (based upon a copper-coordinated tetracarboxylated triphenylbenzene linker), reveals nearly identical properties with BET surface areas in the range of 3300-3500 m(2)/g and excess hydrogen uptake of 5.7 and 5.8 wt % at 77 K. In contrast, adsorption of organosulfur compounds dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (DMDBT) shows remarkably different capacities, providing direct evidence that liquid-phase adsorption is not solely dependent on surface area or linker/metal cluster identity. Structural features present in MCPs derived from these reduced symmetry linkers include the presence of more than one type of Cu-paddlewheel in a structure derived from a terphenyl tricarboxylate (UMCM-151) and a three-bladed zinc paddlewheel metal cluster in an MCP derived from a pentacarboxylated triphenylbenzene linker (UMCM-154).
Schnobrich
Jennifer K
JK
Department of Chemistry and Macromolecular Science and Engineering Program, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109-1055, USA.
Lebel
Olivier
O
Cychosz
Katie A
KA
Dailly
Anne
A
Wong-Foy
Antek G
AG
Matzger
Adam J
AJ
D000327:Adsorption; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry; D016062:Porosity; D013499:Surface Properties
D009942:Organometallic Compounds; D011108:Polymers