A singlet-diradical Co(III)-dimer as a nonvolatile resistive switching device: synthesis, redox-induced interconversion, and current-voltage characteristics
Autor(a) principal: | |
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Data de Publicação: | 2022 |
Outros Autores: | , , , , , , , |
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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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 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
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 |
language |
eng |
dc.relation.none.fl_str_mv |
0002-7863 10.1021/jacs.2c08941 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
American Chemical Society |
publisher.none.fl_str_mv |
American Chemical Society |
dc.source.none.fl_str_mv |
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RCAAP |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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