Excited-state dynamics of heteroleptic copper(i) photosensitizers and their electrochemically reduced forms containing a dipyridophenazine moiety – a spectroelectrochemical transient absorption study

Literature Information

Publication Date 2019-05-07
DOI 10.1039/C9CP00412B
Impact Factor 3.676
Authors

Linda Zedler, Michael Karnahl


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Abstract

The electrochemically singly-reduced Cu(I) photosensitizers of the type [Cu(xant)(N^N)]+ (with xant = xantphos ligand and N^N = bidentate diimine ligand: dipyrido[3,2-a:2′,3′-c]phenazine = dppz or 3,6,11,12-tetramethyl-dipyrido[3,2-a:2′,3′-c]phenazine = tmdppz) exhibit a metal-to-ligand charge transfer (MLCT) transition from the Cu(I) center to the reduced dppz˙− ligand. This special behavior makes them promising candidates for two-electron accumulation. Consequently, the photoinduced excited-state processes of [Cu(xant)(dppz)]+ (1) and [Cu(xant)(tmdppz)]+ (2) were investigated in solution by femtosecond transient absorption spectroelectrochemistry. Furthermore, the influence of the methyl substitution at the dppz ligand on the transient dynamics was revealed. Moreover, both singly-reduced species 1− and 2− possess short-lived excited states (10–20 ps) when excited into the MLCTphen or the low-lying states, representing an obstacle for the possible two-electron photoaccumulation.

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Contents list

Front/Back Matter

DOI: 10.1039/C6CP90269C

Inside front cover

Cover

DOI: 10.1039/C6CP90263D

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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