Merging of the photocatalysis and copper catalysis in metal–organic frameworks for oxidative C–C bond formation† †Electronic supplementary information (ESI) available. CCDC 997028 and 997029. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc02362e Click here for additional data file. Click here for additional data file.

The direct formation of new C–C bonds through photocatalytic oxidative coupling from low reactive sp C–H bonds using environmentally benign and cheap oxygen as oxidant is an important area in sustainable chemistry. By incorporating the photoredox catalyst [SiW11O39Ru(H2O)] 5 into the pores of Cu-based metal–organic frameworks, a new approach for merging Cu-catalysis/Ru-photocatalysis within one single MOF was achieved. The direct Cu–O–W(Ru) bridges made the two metal catalyses being synergetic, enabling the application on the catalysis of the oxidative coupling C–C bond formation from acetophenones and N-phenyl-tetrahydroisoquinoline with excellent conversion and sizeselectivity. The method takes advantage of visible light photoredox catalysis to generate iminium ion intermediate from N-phenyl-tetrahydroisoquinoline under mild conditions and the easy combination with Cu-catalyzed activation of nucleophiles. Control catalytic experiments using similar Cu-based sheets but with the photoredox catalytic anions embedded was also investigated for comparison.