Photoinduced Energy Transfer from Poly(N‐vinylcarbazole) to Tricarbonylchloro‐(2,2′‐bipyridyl)rhenium(I)

Abstract

This work investigates the photoinduced energy transfer from poly(N-vinylcarbazole) (PVK), as a donor material, to fac-(2,2'-bipyridyl)Re(CO)3Cl, as a catalyst acceptor, for its potential application towards CO2 reduction. Photoluminescence quenching experiments reveal dynamic quenching through resonance energy transfer in solid donor/acceptor mixtures and in solid/liquid systems. The bimolecular reaction rate constant at solution–film interfaces for the elementary reaction of the excited state with the quencher material could be determined as 8.8(±1.4)×1011 L mol−1 s−1 by using Stern–Volmer analysis. This work shows that PVK is an effective and cheap absorber material that can act efficiently as a redox photosensitizer in combination with fac-(2,2'-bipyridyl)Re(CO)3Cl as a catalyst acceptor, which might lead to possible applications in photocatalytic CO2 reduction.

Rhenium(i) complexation–dissociation strategy for synthesising fluorine-18 labelled pyridine bidentate radiotracers

“…Further details on the syntheses of the rhenium(I) complexes and the uorinated ligands can be found in Sections S.2 and S.3 of the ESI. † Characterisation data for the rhenium(I) complexes tricarbonylchloro(2,2 0 -bipyridine)rhenium(I) ([Re(CO) 3 (L1a) Cl]), 40,41 tricarbonylchloro(1,10-phenanthroline)rhenium(I) ([Re(CO) 3 (L2a)Cl]) 42 . 19 F{ 1 H} NMR (376 MHz, CD 3 CN, d/ppm): d À56.94.…”

A Beginner's Guide to Organic Semiconductor Photoelectrodes for the Reduction of Carbon Dioxide

“…Energy transfer can be confirmed by looking at the photoluminescence of individual components and comparing them to the mixture thereof. The characteristic photoluminescence peak of PVK at 410 nm has gradually decreased as the concentration of the catalyst (Figure 3), Re‐bipy in the drop‐cast film increased signalling an energy transfer from PVK to Re‐bipy [56] . This study was used as a proof‐of‐concept and CO 2 RR efficiency was not quantified.…”

“…The characteristic photoluminescence peak of PVK at 410 nm has gradually decreased as the concentration of the catalyst (Figure 3), Re-bipy in the dropcast film increased signalling an energy transfer from PVK to Re-bipy. [56] This study was used as a proof-of-concept and CO 2 RR efficiency was not quantified.…”

Construction of a Stable Ru–Re Hybrid System Based on Multifunctional MOF-253 for Efficient Photocatalytic CO2 Reduction

“…[6][7][8][9][10][11] Re I diimine complexes [Re(N, N')(CO)3X] (X=Me, Cl − , etc) have been recognized to be efficient catalysts for CO2 reduction to produce CO or HCOO − via two-electron proton coupled reduction pathways. [12][13][14][15][16][17][18] However, these Re diimine complexes showed poor absorption in visible light region. To be applied in photocatalytic CO2 reduction under visible light, bimetallic M-Re (M=Ru, Ir, Os) supramolecular structures by attaching Re complexes to photosensitizers via covalent bonds should be constructed.…”