Accumulation of Re-complex-based Catalytic Centers in Metal–Organic Cages for Photochemical CO2 Reduction/Insertion

Abstract

Metal–organic cages (MOCs) composed of trinuclear zirconium clusters, Re-complex-based catalyst-incorporated linkers (Lcat), and catalyst-free linkers (L) are synthesized using varying ratios of Lcat and L ([{Cp3Zr3(μ3-O)(μ2-OH)3}4LcatnL6−n]4+ (n = 0.0–5.0, Cp = cyclopentadienyl)). Investigating the catalytic activity of the obtained MOCs revealed that the accumulation of the Re-complex-based catalytic centers affects the photochemical CO2 reduction and CO2 insertion into phenyl vinyl sulfone. Metal-organic cages (MOCs) composed of trinuclear zirconium clusters, Re-complex-based-catalyst-incorporated linkers (Lcat), and catalyst-free linkers (L) were synthesized with various ratios of Lcat and L. The MOCs can serve as catalysts for CO2 reduction and CO2 insertion reactions, and the effect of accumulation of active sites on the photocatalytic activity of MOCs was clarified for the first time.