Cargando…

Chiral Resolution of Spin‐Crossover Active Iron(II) [2x2] Grid Complexes

Chiral magnetic materials are proposed for applications in second‐order non‐linear optics, magneto‐chiral dichroism, among others. Recently, we have reported a set of tetra‐nuclear Fe(II) grid complex conformers with general formula C/S‐[Fe(4)L(4)](8+) (L: 2,6‐bis(6‐(pyrazol‐1‐yl)pyridin‐2‐yl)‐1,5‐d...

Descripción completa

Detalles Bibliográficos
Autores principales: Suryadevara, Nithin, Pausch, Ansgar, Moreno‐Pineda, Eufemio, Mizuno, Asato, Bürck, Jochen, Baksi, Ananya, Hochdörffer, Tim, Šalitroš, Ivan, Ulrich, Anne S., Kappes, Manfred M., Schünemann, Volker, Klopper, Wim, Ruben, Mario
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8597157/
https://www.ncbi.nlm.nih.gov/pubmed/34165834
http://dx.doi.org/10.1002/chem.202101432
_version_ 1784600552984805376
author Suryadevara, Nithin
Pausch, Ansgar
Moreno‐Pineda, Eufemio
Mizuno, Asato
Bürck, Jochen
Baksi, Ananya
Hochdörffer, Tim
Šalitroš, Ivan
Ulrich, Anne S.
Kappes, Manfred M.
Schünemann, Volker
Klopper, Wim
Ruben, Mario
author_facet Suryadevara, Nithin
Pausch, Ansgar
Moreno‐Pineda, Eufemio
Mizuno, Asato
Bürck, Jochen
Baksi, Ananya
Hochdörffer, Tim
Šalitroš, Ivan
Ulrich, Anne S.
Kappes, Manfred M.
Schünemann, Volker
Klopper, Wim
Ruben, Mario
author_sort Suryadevara, Nithin
collection PubMed
description Chiral magnetic materials are proposed for applications in second‐order non‐linear optics, magneto‐chiral dichroism, among others. Recently, we have reported a set of tetra‐nuclear Fe(II) grid complex conformers with general formula C/S‐[Fe(4)L(4)](8+) (L: 2,6‐bis(6‐(pyrazol‐1‐yl)pyridin‐2‐yl)‐1,5‐dihydrobenzo[1,2‐d : 4,5‐d′]diimidazole). In the grid complexes, isomerism emerges from tautomerism and conformational isomerism of the ligand L, and the S‐type grid complex is chiral, which originates from different non‐centrosymmetric spatial organization of the trans type ligand around the Fe(II) center. However, the selective preparation of an enantiomerically pure grid complex in a controlled manner is difficult due to spontaneous self‐assembly. To achieve the pre‐synthesis programmable resolution of Fe(II) grid complexes, we designed and synthesized two novel intrinsically chiral ligands by appending chiral moieties to the parent ligand. The complexation of these chiral ligands with Fe(II) salt resulted in the formation of enantiomerically pure Fe(II) grid complexes, as unambiguously elucidated by CD and XRD studies. The enantiomeric complexes exhibited similar gradual and half‐complete thermal and photo‐induced SCO characteristics. The good agreement between the experimentally obtained and calculated CD spectra further supports the enantiomeric purity of the complexes and even the magnetic studies. The chiral resolution of Fe(II)‐ [2×2] grid complexes reported in this study, for the first time, might enable the fabrication of magneto‐chiral molecular devices.
format Online
Article
Text
id pubmed-8597157
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher John Wiley and Sons Inc.
record_format MEDLINE/PubMed
spelling pubmed-85971572021-11-22 Chiral Resolution of Spin‐Crossover Active Iron(II) [2x2] Grid Complexes Suryadevara, Nithin Pausch, Ansgar Moreno‐Pineda, Eufemio Mizuno, Asato Bürck, Jochen Baksi, Ananya Hochdörffer, Tim Šalitroš, Ivan Ulrich, Anne S. Kappes, Manfred M. Schünemann, Volker Klopper, Wim Ruben, Mario Chemistry Full Papers Chiral magnetic materials are proposed for applications in second‐order non‐linear optics, magneto‐chiral dichroism, among others. Recently, we have reported a set of tetra‐nuclear Fe(II) grid complex conformers with general formula C/S‐[Fe(4)L(4)](8+) (L: 2,6‐bis(6‐(pyrazol‐1‐yl)pyridin‐2‐yl)‐1,5‐dihydrobenzo[1,2‐d : 4,5‐d′]diimidazole). In the grid complexes, isomerism emerges from tautomerism and conformational isomerism of the ligand L, and the S‐type grid complex is chiral, which originates from different non‐centrosymmetric spatial organization of the trans type ligand around the Fe(II) center. However, the selective preparation of an enantiomerically pure grid complex in a controlled manner is difficult due to spontaneous self‐assembly. To achieve the pre‐synthesis programmable resolution of Fe(II) grid complexes, we designed and synthesized two novel intrinsically chiral ligands by appending chiral moieties to the parent ligand. The complexation of these chiral ligands with Fe(II) salt resulted in the formation of enantiomerically pure Fe(II) grid complexes, as unambiguously elucidated by CD and XRD studies. The enantiomeric complexes exhibited similar gradual and half‐complete thermal and photo‐induced SCO characteristics. The good agreement between the experimentally obtained and calculated CD spectra further supports the enantiomeric purity of the complexes and even the magnetic studies. The chiral resolution of Fe(II)‐ [2×2] grid complexes reported in this study, for the first time, might enable the fabrication of magneto‐chiral molecular devices. John Wiley and Sons Inc. 2021-07-20 2021-11-02 /pmc/articles/PMC8597157/ /pubmed/34165834 http://dx.doi.org/10.1002/chem.202101432 Text en © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
Suryadevara, Nithin
Pausch, Ansgar
Moreno‐Pineda, Eufemio
Mizuno, Asato
Bürck, Jochen
Baksi, Ananya
Hochdörffer, Tim
Šalitroš, Ivan
Ulrich, Anne S.
Kappes, Manfred M.
Schünemann, Volker
Klopper, Wim
Ruben, Mario
Chiral Resolution of Spin‐Crossover Active Iron(II) [2x2] Grid Complexes
title Chiral Resolution of Spin‐Crossover Active Iron(II) [2x2] Grid Complexes
title_full Chiral Resolution of Spin‐Crossover Active Iron(II) [2x2] Grid Complexes
title_fullStr Chiral Resolution of Spin‐Crossover Active Iron(II) [2x2] Grid Complexes
title_full_unstemmed Chiral Resolution of Spin‐Crossover Active Iron(II) [2x2] Grid Complexes
title_short Chiral Resolution of Spin‐Crossover Active Iron(II) [2x2] Grid Complexes
title_sort chiral resolution of spin‐crossover active iron(ii) [2x2] grid complexes
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8597157/
https://www.ncbi.nlm.nih.gov/pubmed/34165834
http://dx.doi.org/10.1002/chem.202101432
work_keys_str_mv AT suryadevaranithin chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT pauschansgar chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT morenopinedaeufemio chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT mizunoasato chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT burckjochen chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT baksiananya chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT hochdorffertim chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT salitrosivan chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT ulrichannes chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT kappesmanfredm chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT schunemannvolker chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT klopperwim chiralresolutionofspincrossoveractiveironii2x2gridcomplexes
AT rubenmario chiralresolutionofspincrossoveractiveironii2x2gridcomplexes