International Summer School PROGRAM - Laboratoire d'Infochimie ...

Mirco- and Mesoporous Coordination Polymers: Synthesis, Structure
and Properties
Vladimir P. Fedin
Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Novosibirsk, Russia
Synthesis, structure and functional properties of microporous and mesoporous metal-
organic coordination polymers will be considered. Hybrid MIL-101/polyoxotungstate
materials were used for selective oxidation of a range of alkenes with aqueous hydrogen
peroxide. The selectivities toward epoxides were comparable or even superior to the
corresponding homogeneous polyoxotungstates and strongly depended on the alkene
nature. Under the reaction conditions employed, the hybrid materials were stable to
leaching, behaved as true heterogeneous catalysts and could be used repeatedly several
times without suffering a loss of the activity and selectivity.
Enantiopure (homochiral) porous absorbents provide great opportunities for
stereoselective sorption of chiral guest molecules and therefore highly demanded for
separation and purification of important substrates including drugs and other bioactive
molecules. Porous homochiral coordination polymers represent promising class of
porous chiral absorbents due to high versatility of structural design; however the
synthetic accessibility still remains a challenging problem here. Starting from
enantiopure lactic, mandelic, camphoric, malic and aspartic acids we obtained series of
homochiral porous coordination polymers with isoreticular topologies. These structures
share the same building chiral motif with rigid linkers controlling the important
structural properties (the pore sizes, free accessible volumes) and stability of the metal-
organic frameworks upon guest exchange. These structures were shown to possess
remarkable size- and enantioselective sorption properties toward chiral alcohols and sulfoxides.
More important, some chiral drug precursors also show notable enantioselectivity upon
inclusion into these homochiral porous coordination polymers.
The research was partially supported by the Russian Foundation for Basic Research
(11-03-00112) and Russian Academy of Sciences (program 5.6.1).