Abstract
Two multi-Rh-incorporated polyoxometalates [NH2(CH3)2]10[Na4(H2O)8]H3[As4W42O142(OH)4(CH3COO)2Rh3(H2O)4]·13H2O·4[NH(CH3)2] (1) and [K4Na(H2O)6]KH10[As4W40O140Rh4(H2O)4]·34H2O (2) have been synthesized in acetate buffer solution. Polyanion 1a is built up atop of an acetate-modified rectangular framework [As4W42O142(OH)4(CH3COO)2]26-, while polyanion 2a contains a pure inorganic cryptand [As4W40O140]28-. All Rh atoms of these two compounds share the same hexa-coordinate distorted-octahedral geometry and are embedded into their cavities through As-Rh bonding with a bond length around 2.304(4)-2.436(5) Å. Besides, they not only represent structural novelty but also demonstrate controllable proton conduction properties. Catalysts 1 and 2 can catalyze cycloaddition of epoxides with CO2 in a solvent-free system in conjunction with 1-ethyl-1-methylpyrrolidinium bromide.
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