Bright or Dark: Unexpected Photocatalytic Behavior of Closely Related Phenanthroline‐based Copper(I) Photosensitizers

Author:

Doettinger Florian1ORCID,Obermeier Martin2,Caliskanyürek Volkan1ORCID,Burmeister Lars E.1ORCID,Kleeberg Christian3,Karnahl Michael1ORCID,Schwalbe Matthias4ORCID,Tschierlei Stefanie1ORCID

Affiliation:

1. Department of Energy Conversion Institute of Physical and Theoretical Chemistry Technische Universität Braunschweig Rebenring 31 38106 Braunschweig Germany

2. Department of Chemistry Humboldt-Universität zu Berlin Brook-Taylor-Str. 2 12489 Berlin Germany

3. Institute of Inorganic and Analytical Chemistry Technische Universität Braunschweig Hagenring 30 38106 Braunschweig Germany

4. Department of Chemistry Faculty of Science Utrecht University Budapestlaan 4b 3584 CD Utrecht The Netherlands

Abstract

AbstractIn search of a better understanding of the structure‐property relationship of heteroleptic CuI photosensitizers, two structurally closely related complexes are investigated in detail. Although both compounds bear the same 4‐methoxyphenyl substituents at the phenanthroline moiety (i. e. at 5,6‐position in Cu1 and at 4,7‐position in Cu2), substitution at the 4,7‐position increases the attenuation coefficient in the 300–500 nm range by a factor of more than two. Even more drastic is the difference in emission lifetime (11 vs. 628 ns), which rises by a factor of almost 60 when positions 4 and 7 (i. e. Cu2) are chosen. A combination of solid‐state structural analysis, TDDFT calculations, transient absorption spectroscopy and quenching studies is then applied to elucidate the reasons for the superior photophysical properties of Cu2. Subsequently, a non‐emissive and long‐lived excited state (715 ns) has been revealed for Cu1. In a next step, both complexes were successfully used in the photocatalytic splitting of water and the reduction of CO2 to CO to test the influence of this behavior on the activity. Most importantly, Cu2 not only performs significantly better than Cu1, but also than the benchmark system and the noble‐metal‐based complex [Ir(dFppy)3].

Publisher

Wiley

Subject

Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Catalysis

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