A singlet-diradical Co(III)-dimer as a nonvolatile resistive switching device: synthesis, redox-induced interconversion, and current-voltage characteristics

Detalhes bibliográficos
Autor(a) principal: Sinha, Suman
Data de Publicação: 2022
Outros Autores: Sahad E, Muhammed, Mondal, Rakesh, Das, Siuli, Manamel, Litty Thomas, Brandão, Paula, de Bruin, Bas, Das, Bikas C., Paul, Nanda D.
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10773/36481
Resumo: Herein we report a ligand-centered redox-controlled strategy for the synthesis of an unusual binuclear diradical cobalt(III) complex, [Co2III(L•3-)2] (1), featuring two three-electron reduced trianionic monoradical 2,9-bis(phenyldiazo)-1,10-phenanthroline ligands (L•3-) and two intermediate-spin cobalt(III) centers having a Co-Co bond. Controlled ligand-centered oxidation of 1 afforded two mononuclear complexes, [CoII(L•-)(L0)]+ ([3])+ and [CoII(L0)2]2+ ([2]2+), which upon further ligand-centered reduction yielded a di-azo-anion diradical complex, [CoII(L•-)2] (4). In complex 1, two three-electron reduced di-azo-anion monoradical ligands (L•3-) bridge two intermediate Co(III) centers at a distance of 2.387(2) Å, while upon oxidation, one of the coordinating azo-arms of L becomes pendent, and in complexes [2]2+, [3]+, and 4, two tetradentate ligands coordinate a single Co(II) center in a tridentate meridional fashion with one uncoordinated azo-arm from each of the ligands. In the presence of reducing agents, the monomers [2]2+, [3]+, and 4 undergo ligand-centered reduction to form azo-anion radicals, and the otherwise pendent azo-arms in the presence of cobalt(II)-salts like Co(ClO4)2 or CoCl2 bind the second Co(II)-ion; further internal electron transfer from the cobalt center to the arylazo backbone produces the binuclear complex 1. Spectroscopic analysis, DFT studies, and control experiments were performed to understand the electronic structures and the ligand-centered redox-controlled interconversion. The application of complex 1 as a molecular memory device (memristor) was also explored. Complex 1 showed encouraging results as a memristor with a current ON/OFF ratio > 104 and is highly promising for resistive RAM/ROM applications.
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spelling A singlet-diradical Co(III)-dimer as a nonvolatile resistive switching device: synthesis, redox-induced interconversion, and current-voltage characteristicsHerein we report a ligand-centered redox-controlled strategy for the synthesis of an unusual binuclear diradical cobalt(III) complex, [Co2III(L•3-)2] (1), featuring two three-electron reduced trianionic monoradical 2,9-bis(phenyldiazo)-1,10-phenanthroline ligands (L•3-) and two intermediate-spin cobalt(III) centers having a Co-Co bond. Controlled ligand-centered oxidation of 1 afforded two mononuclear complexes, [CoII(L•-)(L0)]+ ([3])+ and [CoII(L0)2]2+ ([2]2+), which upon further ligand-centered reduction yielded a di-azo-anion diradical complex, [CoII(L•-)2] (4). In complex 1, two three-electron reduced di-azo-anion monoradical ligands (L•3-) bridge two intermediate Co(III) centers at a distance of 2.387(2) Å, while upon oxidation, one of the coordinating azo-arms of L becomes pendent, and in complexes [2]2+, [3]+, and 4, two tetradentate ligands coordinate a single Co(II) center in a tridentate meridional fashion with one uncoordinated azo-arm from each of the ligands. In the presence of reducing agents, the monomers [2]2+, [3]+, and 4 undergo ligand-centered reduction to form azo-anion radicals, and the otherwise pendent azo-arms in the presence of cobalt(II)-salts like Co(ClO4)2 or CoCl2 bind the second Co(II)-ion; further internal electron transfer from the cobalt center to the arylazo backbone produces the binuclear complex 1. Spectroscopic analysis, DFT studies, and control experiments were performed to understand the electronic structures and the ligand-centered redox-controlled interconversion. The application of complex 1 as a molecular memory device (memristor) was also explored. Complex 1 showed encouraging results as a memristor with a current ON/OFF ratio > 104 and is highly promising for resistive RAM/ROM applications.American Chemical Society2022-01-01T00:00:00Z2022-11-09T00:00:00Z2022-11-09info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10773/36481eng0002-786310.1021/jacs.2c08941Sinha, SumanSahad E, MuhammedMondal, RakeshDas, SiuliManamel, Litty ThomasBrandão, Paulade Bruin, BasDas, Bikas C.Paul, Nanda D.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-02-22T12:09:49Zoai:ria.ua.pt:10773/36481Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-20T03:07:05.143781Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse
dc.title.none.fl_str_mv A singlet-diradical Co(III)-dimer as a nonvolatile resistive switching device: synthesis, redox-induced interconversion, and current-voltage characteristics
title A singlet-diradical Co(III)-dimer as a nonvolatile resistive switching device: synthesis, redox-induced interconversion, and current-voltage characteristics
spellingShingle A singlet-diradical Co(III)-dimer as a nonvolatile resistive switching device: synthesis, redox-induced interconversion, and current-voltage characteristics
Sinha, Suman
title_short A singlet-diradical Co(III)-dimer as a nonvolatile resistive switching device: synthesis, redox-induced interconversion, and current-voltage characteristics
title_full A singlet-diradical Co(III)-dimer as a nonvolatile resistive switching device: synthesis, redox-induced interconversion, and current-voltage characteristics
title_fullStr A singlet-diradical Co(III)-dimer as a nonvolatile resistive switching device: synthesis, redox-induced interconversion, and current-voltage characteristics
title_full_unstemmed A singlet-diradical Co(III)-dimer as a nonvolatile resistive switching device: synthesis, redox-induced interconversion, and current-voltage characteristics
title_sort A singlet-diradical Co(III)-dimer as a nonvolatile resistive switching device: synthesis, redox-induced interconversion, and current-voltage characteristics
author Sinha, Suman
author_facet Sinha, Suman
Sahad E, Muhammed
Mondal, Rakesh
Das, Siuli
Manamel, Litty Thomas
Brandão, Paula
de Bruin, Bas
Das, Bikas C.
Paul, Nanda D.
author_role author
author2 Sahad E, Muhammed
Mondal, Rakesh
Das, Siuli
Manamel, Litty Thomas
Brandão, Paula
de Bruin, Bas
Das, Bikas C.
Paul, Nanda D.
author2_role author
author
author
author
author
author
author
author
dc.contributor.author.fl_str_mv Sinha, Suman
Sahad E, Muhammed
Mondal, Rakesh
Das, Siuli
Manamel, Litty Thomas
Brandão, Paula
de Bruin, Bas
Das, Bikas C.
Paul, Nanda D.
description Herein we report a ligand-centered redox-controlled strategy for the synthesis of an unusual binuclear diradical cobalt(III) complex, [Co2III(L•3-)2] (1), featuring two three-electron reduced trianionic monoradical 2,9-bis(phenyldiazo)-1,10-phenanthroline ligands (L•3-) and two intermediate-spin cobalt(III) centers having a Co-Co bond. Controlled ligand-centered oxidation of 1 afforded two mononuclear complexes, [CoII(L•-)(L0)]+ ([3])+ and [CoII(L0)2]2+ ([2]2+), which upon further ligand-centered reduction yielded a di-azo-anion diradical complex, [CoII(L•-)2] (4). In complex 1, two three-electron reduced di-azo-anion monoradical ligands (L•3-) bridge two intermediate Co(III) centers at a distance of 2.387(2) Å, while upon oxidation, one of the coordinating azo-arms of L becomes pendent, and in complexes [2]2+, [3]+, and 4, two tetradentate ligands coordinate a single Co(II) center in a tridentate meridional fashion with one uncoordinated azo-arm from each of the ligands. In the presence of reducing agents, the monomers [2]2+, [3]+, and 4 undergo ligand-centered reduction to form azo-anion radicals, and the otherwise pendent azo-arms in the presence of cobalt(II)-salts like Co(ClO4)2 or CoCl2 bind the second Co(II)-ion; further internal electron transfer from the cobalt center to the arylazo backbone produces the binuclear complex 1. Spectroscopic analysis, DFT studies, and control experiments were performed to understand the electronic structures and the ligand-centered redox-controlled interconversion. The application of complex 1 as a molecular memory device (memristor) was also explored. Complex 1 showed encouraging results as a memristor with a current ON/OFF ratio > 104 and is highly promising for resistive RAM/ROM applications.
publishDate 2022
dc.date.none.fl_str_mv 2022-01-01T00:00:00Z
2022-11-09T00:00:00Z
2022-11-09
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dc.identifier.uri.fl_str_mv http://hdl.handle.net/10773/36481
url http://hdl.handle.net/10773/36481
dc.language.iso.fl_str_mv eng
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dc.relation.none.fl_str_mv 0002-7863
10.1021/jacs.2c08941
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dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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