Issue 5, 2017

Photoinduced electron transfer from rylenediimide radical anions and dianions to Re(bpy)(CO)3 using red and near-infrared light

Abstract

A major goal of artificial photosynthesis research is photosensitizing highly reducing metal centers using as much as possible of the solar spectrum reaching Earth's surface. The radical anions and dianions of rylenediimide (RDI) dyes, which absorb at wavelengths as long as 950 nm, are powerful photoreductants with excited state oxidation potentials that rival or exceed those of organometallic chromophores. These dyes have been previously incorporated into all-organic donor–acceptor systems, but have not yet been shown to reduce organometallic centers. This study describes a set of dyads in which perylenediimide (PDI) or naphthalenediimide (NDI) chromophores are attached to Re(bpy)(CO)3 through either the bipyridine ligand or more directly to the Re center via a pyridine ligand. The chromophores are reduced with a mild reducing agent, after which excitation with long-wavelength red or near-infrared light leads to reduction of the Re complex. The kinetics of electron transfer from the photoexcited anions to the Re complex are monitored using transient visible/near-IR and mid-IR spectroscopy, complemented by theoretical spectroscopic assignments. The photo-driven charge shift from the reduced PDI or NDI to the complex occurs in picoseconds regardless of whether PDI or NDI is attached to the bipyridine or to the Re center, but back electron transfer is found to be three orders of magnitude slower with the chromophore attached to the Re center. These results will inform the design of future catalytic systems that incorporate RDI anions as chromophores.

Graphical abstract: Photoinduced electron transfer from rylenediimide radical anions and dianions to Re(bpy)(CO)3 using red and near-infrared light

Supplementary files

Article information

Article type
Edge Article
Submitted
19 noy 2016
Accepted
27 fev 2017
First published
28 fev 2017
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., 2017,8, 3821-3831

Photoinduced electron transfer from rylenediimide radical anions and dianions to Re(bpy)(CO)3 using red and near-infrared light

N. T. La Porte, J. F. Martinez, S. Hedström, B. Rudshteyn, B. T. Phelan, C. M. Mauck, R. M. Young, V. S. Batista and M. R. Wasielewski, Chem. Sci., 2017, 8, 3821 DOI: 10.1039/C6SC05103K

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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