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Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties

Harsh Bhatia, Junjun Guo, Chris Savory Orcid Logo, Martyn Rush, David Ian James, Avishek Dey, Charles Chen, Dejan-Krešimir Bučar Orcid Logo, Tracey M. Clarke Orcid Logo, David O. Scanlon Orcid Logo, Robert G. Palgrave Orcid Logo, Bob C. Schroeder Orcid Logo

Inorganic Chemistry, Volume: 63, Issue: 1, Pages: 416 - 430

Swansea University Author: Chris Savory Orcid Logo

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DOI (Published version): 10.1021/acs.inorgchem.3c03290

Abstract

Bismuth-based coordination complexes are advantageous over other metal complexes, as bismuth is the heaviest nontoxic element with high spin–orbit coupling and potential optoelectronics applications. Herein, four bismuth halide-based coordination complexes [Bi2Cl6(phen-thio)2] (1), [Bi2Br6(phen-thio...

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Published in: Inorganic Chemistry
ISSN: 0020-1669 1520-510X
Published: American Chemical Society (ACS) 2024
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URI: https://cronfa.swan.ac.uk/Record/cronfa70857
Abstract: Bismuth-based coordination complexes are advantageous over other metal complexes, as bismuth is the heaviest nontoxic element with high spin–orbit coupling and potential optoelectronics applications. Herein, four bismuth halide-based coordination complexes [Bi2Cl6(phen-thio)2] (1), [Bi2Br6(phen-thio)2] (2), [Bi2I6(phen-thio)2] (3), and [Bi2I6(phen-Me)2] (4) were synthesized, characterized, and subjected to detailed photophysical studies. The complexes were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and NMR studies. Spectroscopic analyses of 1–4 in solutions of different polarities were performed to understand the role of the organic and inorganic components in determining the ground- and excited-state properties of the complexes. The photophysical properties of the complexes were characterized by ground-state absorption, steady-state photoluminescence, microsecond time-resolved photoluminescence, and absorption spectroscopy. Periodic density functional theory (DFT) calculations were performed on the solid-state structures to understand the role of the organic and inorganic parts of the complexes. The studies showed that changing the ancillary ligand from chlorine (Cl) and bromine (Br) to iodine (I) bathochromically shifts the absorption band along with enhancing the absorption coefficient. Also, changing the halides (Cl, Br to I) affects the photoluminescent quantum yields of the ligand-centered (LC) emissive state without markedly affecting the lifetimes. The combined results confirmed that ground-state properties are strongly influenced by the inorganic part, and the lower-energy excited state is LC. This study paves the way to design novel bismuth coordination complexes for optoelectronic applications by rigorously choosing the ligands and bismuth salt.
College: Faculty of Science and Engineering
Funders: This research has been supported by the UKRI Innovate UK (Grant No: 56338). C.N.S. acknowledges the Ramsay Memorial Fellowship Trust and UCL Department of Chemistry for the funding of a Ramsay Memorial Fellowship. The use of the UCL Myriad and Kathleen High-Performance Computing Facilities (Myriad@UCL and Kathleen@UCL) is acknowledged in the production of this work. The use of the ARCHER and ARCHER2 UK National Supercomputing Services via our membership of the UK’s HEC Materials Chemistry Consortium, funded by EPSRC (EP/R029431, EP/ X035859), is also acknowledged. The X-ray photoelectron (XPS) data collection was performed at the EPSRC National Facility for XPS (“HarwellXPS”), operated by Cardiff University and UCL, under contract no. PR16195. B.C.S. acknowledges the UKRI for Future Leaders Fellowship no. MR/S031952/1.
Issue: 1
Start Page: 416
End Page: 430

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