The Coordination Behaviour of CuI Photosensitizers Bearing Multidentate Ligands Investigated by X-ray Absorption Spectroscopy

Rentschler, Martin; Iglesias, Sirma; Schmid, Marie‐Ann; Liu, Cunming; Tschierlei, Stefanie; Frey, Wolfgang; Zhang, Xiaoyi; Karnahl, Michael; Moonshiram, Dooshaye

doi:10.1002/chem.201905601

Title: The Coordination Behaviour of Cu^I Photosensitizers Bearing Multidentate Ligands Investigated by X-ray Absorption Spectroscopy

Journal Article · 12 March 2020 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.201905601 · OSTI ID:1658815

Rentschler, Martin ^[1]; Iglesias, Sirma ^[2]; Schmid, Marie‐Ann ^[3]; Liu, Cunming ^[4];

^[3]; Frey, Wolfgang ^[1]; Zhang, Xiaoyi ^[4];

^[1];

^[2]

Univ. of Stuttgart (Germany)
IMDEA Nanosciencia, Madrid (Spain)
Ulm Univ. (Germany)
Argonne National Lab. (ANL), Argonne, IL (United States)

A systematic series of four novel homo- and heteroleptic Cu(I)photosensitizers based on tetradentate 1,10-phenanthroline ligands of the type X^N^N^X containing two additional donor moieties in the 2,9-position (X=SMe or OMe) were designed. Their solid-state structures were assessed by X-ray diffraction. Cyclic voltammetry, UV-vis absorption, emission and X-ray absorption spectroscopy were then used to determine their electrochemical, photophysical and structural features in solution. Following, time-resolved X-ray absorption spectroscopy in the picosecond time scale, coupled with time-dependent density functional theory calculations, provided in-depth information on the excited state electron configurations. For the first time, a significant shortening of the Cu-X distance and a change in the coordination mode to a pentacoordinated geometry is shown in the excited states of the two homoleptic complexes. These findings are important with respect to a precise understanding of the excited state structures and a further stabilization of this type of photosensitizers.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); IMDEA Nanoscience Inst., Madrid (Spain); Univ. of Stuttgart (Germany)

Sponsoring Organization:: USDOE Office of Science (SC); German Research Foundation (DFG); Instituto IMDEA Nanociencia; Acciones de Dinamizacijn Europa Investigacion; Spanish Ministerio de Ciencia; Baden- Werttemberg Foundation; Ayudante de Investigacion; Ministry of Science and Innovation (Spain); Community of Madrid (Spain)

Grant/Contract Number:: AC02-06CH11357; SEV-2016-0686; EIN2019-103399; PID2019-111086RA-I00; TS 330/4-1; KA 4671/2-1; TS 330/3-1; PEJ-2019-AI/AMB-13038

OSTI ID:: 1658815

Alternate ID(s):: OSTI ID: 1646610

Journal Information:: Chemistry - A European Journal, Vol. 26, Issue 43; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 13 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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CCDC 1970787: Experimental Crystal Structure Determination Martin, Rentschler,; Sirma, Iglesias,; Marie-Ann, Schmid, https://doi.org/10.5517/ccdc.csd.cc244rsv The current record is supplemented by this dataset	dataset	January 2020
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Title: The Coordination Behaviour of CuI Photosensitizers Bearing Multidentate Ligands Investigated by X-ray Absorption Spectroscopy

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