Issue 11, 2016

Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction

Abstract

We developed new cyclic Re(I)-based trinuclear redox photosensitizers with both high oxidation power in the excited state and strong reduction power in the reduced form. These excellent properties were achieved by introducing electron-donating groups on the diimine ligand of the Re(I) metal centre and by connecting each Re(I) unit with polyphenyl–bisphosphine bridging ligands. These Re-rings were applied to homogenous visible light-driven photocatalytic CO2 reduction in conjunction with various mononuclear catalysts, such as Re(I), Ru(II) and Mn(I) metal complexes, employing a relatively weak sacrificial electron donor, triethanolamine. Each system showed good product selectivity (CO or HCOOH) and an excellent quantum yield of product formation ΦCO = 0.60 to 0.74 using fac-[ReI(bpy)(CO)3(CH3CN)]+, ΦHCOOH = 0.58 using trans(Cl)–RuII(dtbb)(CO)2Cl2 and ΦHCOOH = 0.48 using a fac-[MnI(dtbb)(CO)3(CH3CN)]+ catalyst. The high photocatalytic efficiencies for CO2 reduction are attributed to efficient reductive quenching of the Re-ring by triethanolamine and fast electron transfer from the generated one-electron-reduced species of the ring to the catalyst.

Graphical abstract: Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction

Supplementary files

Article information

Article type
Edge Article
Submitted
02 May 2016
Accepted
04 Jul 2016
First published
05 Jul 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2016,7, 6728-6739

Rhenium(I) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction

J. Rohacova and O. Ishitani, Chem. Sci., 2016, 7, 6728 DOI: 10.1039/C6SC01913G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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