Effect of pore sizes on catalytic activities of arenetricarbonyl metal complexes constructed within Zr-based MOFsElectronic supplementary information (ESI) available: Experimental procedures; FT-IR spectra of UiO-66-Cr(CO)3 and UiO-67-Cr(CO)3; time course of epoxidation of cyclooctene; leaching test; and chemical stability of UiO-67-Mo(CO)3 structure. See DOI: 10.1039/c3dt50593f

Arenetricarbonyl metal complexes ([phM(CO) 3 ] and [biphM(CO) 3 ]; ph = phenylene, biph = biphenylene, M = Mo, Cr) constructed within Zr-based MOFs act as highly active and selective catalysts for epoxidation of cyclooctene. Catalytic activities of these complexes are enhanced with increasing the pore sizes of Zr-based MOFs. Arenetricarbonyl complexes constructed within UiO-67 exhibited higher catalytic activities than those within UiO-66 due to the effective substance diffusion attributable to large pores of UiO-67.