Copper(i) pyrimidine-2-thiolate cluster-based polymers as bifunctional visible-light-photocatalysts for chemoselective transfer hydrogenation of α,β-unsaturated carbonyls.

The photoinduced chemoselective transfer hydrogenation of unsaturated carbonyls to allylic alcohols has been accomplished using cluster-based MOFs as bifunctional visible photocatalysts. Assemblies of hexanuclear clusters [Cu6(dmpymt)6] (1, Hdmpymt = 4,6-dimethylpyrimidine-2-thione) as metalloligands with CuI or (Ph3P)CuI yielded cluster-based metal organic frameworks (MOFs) {[Cu6(dmpymt)6]2[Cu2(μ-I)2]4(CuI)2} n (2), {[Cu6(dmpymt)6]2[Cu2(μ-I)2]4} n (3), respectively. Nanoparticles (NPs) of 2 and 3 served both as photosensitizers and photocatalysts for the highly chemoselective reduction of unsaturated carbonyl compounds to unsaturated alcohols with high catalytic activity under blue LED irradiation. The photocatalytic system could be reused for several cycles without any obvious loss of efficiency.