No Cover Image

Journal article 54 views 4 downloads

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

  • 70857.VoR.pdf

    PDF | Version of Record

    © 2023 The Authors. This publication is licensed under a CC-BY 4.0 licence.

    Download (5.73MB)

Check full text

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...

Full description

Published in: Inorganic Chemistry
ISSN: 0020-1669 1520-510X
Published: American Chemical Society (ACS) 2024
Online Access: Check full text

URI: https://cronfa.swan.ac.uk/Record/cronfa70857
first_indexed 2025-11-06T22:01:34Z
last_indexed 2026-01-09T05:31:29Z
id cronfa70857
recordtype SURis
fullrecord <?xml version="1.0"?><rfc1807><datestamp>2026-01-08T15:37:18.7361908</datestamp><bib-version>v2</bib-version><id>70857</id><entry>2025-11-06</entry><title>Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties</title><swanseaauthors><author><sid>1951890f7d79de7d173a378c5dc17bca</sid><ORCID>0000-0002-9052-7484</ORCID><firstname>Chris</firstname><surname>Savory</surname><name>Chris Savory</name><active>true</active><ethesisStudent>false</ethesisStudent></author></swanseaauthors><date>2025-11-06</date><deptcode>EAAS</deptcode><abstract>Bismuth-based coordination complexes are advantageous over other metal complexes, as bismuth is the heaviest nontoxic element with high spin&#x2013;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&#x2013;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.</abstract><type>Journal Article</type><journal>Inorganic Chemistry</journal><volume>63</volume><journalNumber>1</journalNumber><paginationStart>416</paginationStart><paginationEnd>430</paginationEnd><publisher>American Chemical Society (ACS)</publisher><placeOfPublication/><isbnPrint/><isbnElectronic/><issnPrint>0020-1669</issnPrint><issnElectronic>1520-510X</issnElectronic><keywords/><publishedDay>8</publishedDay><publishedMonth>1</publishedMonth><publishedYear>2024</publishedYear><publishedDate>2024-01-08</publishedDate><doi>10.1021/acs.inorgchem.3c03290</doi><url/><notes/><college>COLLEGE NANME</college><department>Engineering and Applied Sciences School</department><CollegeCode>COLLEGE CODE</CollegeCode><DepartmentCode>EAAS</DepartmentCode><institution>Swansea University</institution><apcterm>Another institution paid the OA fee</apcterm><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&#x2019;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 (&#x201C;HarwellXPS&#x201D;), operated by Cardiff University and UCL, under contract no. PR16195. B.C.S. acknowledges the UKRI for Future Leaders Fellowship no. MR/S031952/1.</funders><projectreference/><lastEdited>2026-01-08T15:37:18.7361908</lastEdited><Created>2025-11-06T16:49:32.7633912</Created><path><level id="1">Faculty of Science and Engineering</level><level id="2">School of Engineering and Applied Sciences - Chemistry</level></path><authors><author><firstname>Harsh</firstname><surname>Bhatia</surname><order>1</order></author><author><firstname>Junjun</firstname><surname>Guo</surname><order>2</order></author><author><firstname>Chris</firstname><surname>Savory</surname><orcid>0000-0002-9052-7484</orcid><order>3</order></author><author><firstname>Martyn</firstname><surname>Rush</surname><order>4</order></author><author><firstname>David Ian</firstname><surname>James</surname><order>5</order></author><author><firstname>Avishek</firstname><surname>Dey</surname><order>6</order></author><author><firstname>Charles</firstname><surname>Chen</surname><order>7</order></author><author><firstname>Dejan-Kre&#x161;imir</firstname><surname>Bu&#x10D;ar</surname><orcid>0000-0001-6393-276x</orcid><order>8</order></author><author><firstname>Tracey M.</firstname><surname>Clarke</surname><orcid>0000-0003-4943-0645</orcid><order>9</order></author><author><firstname>David O.</firstname><surname>Scanlon</surname><orcid>0000-0001-9174-8601</orcid><order>10</order></author><author><firstname>Robert G.</firstname><surname>Palgrave</surname><orcid>0000-0003-4522-2486</orcid><order>11</order></author><author><firstname>Bob C.</firstname><surname>Schroeder</surname><orcid>0000-0002-9793-631x</orcid><order>12</order></author></authors><documents><document><filename>70857__35933__131ac4c38e9445b48f5d967d7c5a5d2e.pdf</filename><originalFilename>70857.VoR.pdf</originalFilename><uploaded>2026-01-08T15:17:05.7599104</uploaded><type>Output</type><contentLength>6010650</contentLength><contentType>application/pdf</contentType><version>Version of Record</version><cronfaStatus>true</cronfaStatus><documentNotes>&#xA9; 2023 The Authors. This publication is licensed under a CC-BY 4.0 licence.</documentNotes><copyrightCorrect>true</copyrightCorrect><language>eng</language><licence>https://creativecommons.org/licenses/by/4.0/</licence></document></documents><OutputDurs/></rfc1807>
spelling 2026-01-08T15:37:18.7361908 v2 70857 2025-11-06 Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties 1951890f7d79de7d173a378c5dc17bca 0000-0002-9052-7484 Chris Savory Chris Savory true false 2025-11-06 EAAS 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. Journal Article Inorganic Chemistry 63 1 416 430 American Chemical Society (ACS) 0020-1669 1520-510X 8 1 2024 2024-01-08 10.1021/acs.inorgchem.3c03290 COLLEGE NANME Engineering and Applied Sciences School COLLEGE CODE EAAS Swansea University Another institution paid the OA fee 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. 2026-01-08T15:37:18.7361908 2025-11-06T16:49:32.7633912 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Harsh Bhatia 1 Junjun Guo 2 Chris Savory 0000-0002-9052-7484 3 Martyn Rush 4 David Ian James 5 Avishek Dey 6 Charles Chen 7 Dejan-Krešimir Bučar 0000-0001-6393-276x 8 Tracey M. Clarke 0000-0003-4943-0645 9 David O. Scanlon 0000-0001-9174-8601 10 Robert G. Palgrave 0000-0003-4522-2486 11 Bob C. Schroeder 0000-0002-9793-631x 12 70857__35933__131ac4c38e9445b48f5d967d7c5a5d2e.pdf 70857.VoR.pdf 2026-01-08T15:17:05.7599104 Output 6010650 application/pdf Version of Record true © 2023 The Authors. This publication is licensed under a CC-BY 4.0 licence. true eng https://creativecommons.org/licenses/by/4.0/
title Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties
spellingShingle Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties
Chris Savory
title_short Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties
title_full Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties
title_fullStr Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties
title_full_unstemmed Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties
title_sort Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties
author_id_str_mv 1951890f7d79de7d173a378c5dc17bca
author_id_fullname_str_mv 1951890f7d79de7d173a378c5dc17bca_***_Chris Savory
author Chris Savory
author2 Harsh Bhatia
Junjun Guo
Chris Savory
Martyn Rush
David Ian James
Avishek Dey
Charles Chen
Dejan-Krešimir Bučar
Tracey M. Clarke
David O. Scanlon
Robert G. Palgrave
Bob C. Schroeder
format Journal article
container_title Inorganic Chemistry
container_volume 63
container_issue 1
container_start_page 416
publishDate 2024
institution Swansea University
issn 0020-1669
1520-510X
doi_str_mv 10.1021/acs.inorgchem.3c03290
publisher American Chemical Society (ACS)
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemistry{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemistry
document_store_str 1
active_str 0
description 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.
published_date 2024-01-08T05:33:47Z
_version_ 1856987021140033536
score 11.096068

Similar Items