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Structural dynamics of a thermally silent triiron(ii) spin crossover defect grid complex
The structural evolution of spin crossover (SCO) complexes during their spin transition at equilibrium and out-of-equilibrium conditions needs to be understood to enable their successful utilisation in displays, actuators and memory components. In this study, diffraction techniques were employed to...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10498823/ https://www.ncbi.nlm.nih.gov/pubmed/37656445 http://dx.doi.org/10.1039/d3dt02067c |
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author | Velazquez-Garcia, Jose de Jesus Basuroy, Krishnayan Storozhuk, Darina Wong, Joanne Demeshko, Serhiy Meyer, Franc Henning, Robert Techert, Simone |
author_facet | Velazquez-Garcia, Jose de Jesus Basuroy, Krishnayan Storozhuk, Darina Wong, Joanne Demeshko, Serhiy Meyer, Franc Henning, Robert Techert, Simone |
author_sort | Velazquez-Garcia, Jose de Jesus |
collection | PubMed |
description | The structural evolution of spin crossover (SCO) complexes during their spin transition at equilibrium and out-of-equilibrium conditions needs to be understood to enable their successful utilisation in displays, actuators and memory components. In this study, diffraction techniques were employed to study the structural changes accompanying the temperature increase and the light irradiation of a defect [2 × 2] triiron(ii) metallogrid of the form [Fe(II)(3)L(H)(2)(HL(H))(2)](BF(4))(4)·4MeCN (FE3), L(H) = 3,5-bis{6-(2,2′-bipyridyl)}pyrazole. Although a multi-temperature crystallographic investigation on single crystals evidenced that the compound does not exhibit a thermal spin transition, the structural analysis of the defect grid suggests that the flexibility of the grid, provided by a metal-devoid vertex, leads to interesting characteristics that can be used for intermolecular cooperativity in related thermally responsive systems. Time-resolved photocrystallography results reveal that upon excitation with a ps laser pulse, the defect grid shows the first two steps of the out-of-equilibrium process, namely the photoinduced and elastic steps, occurring at the ps and ns time scales, respectively. Similar to a previously reported [2 × 2] tetrairon(ii) metallogrid, FE3 exhibits a local distortion of the entire grid during the photoinduced step and a long-range distortion of the lattice during the elastic step. Although the lifetime of the pure photoinduced high spin (HS) state is longer in the tetranuclear grid than in the defect grid, suggesting that the global nuclearity plays a crucial role for the lifetime of the photoinduced species, the influence of the co-crystalising solvent on the lifetime of the photoinduced HS state remains unknown. This study sheds light on the out-of-equilibrium dynamics of a thermally silent defect triiron SCO metallogrid. |
format | Online Article Text |
id | pubmed-10498823 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-104988232023-09-14 Structural dynamics of a thermally silent triiron(ii) spin crossover defect grid complex Velazquez-Garcia, Jose de Jesus Basuroy, Krishnayan Storozhuk, Darina Wong, Joanne Demeshko, Serhiy Meyer, Franc Henning, Robert Techert, Simone Dalton Trans Chemistry The structural evolution of spin crossover (SCO) complexes during their spin transition at equilibrium and out-of-equilibrium conditions needs to be understood to enable their successful utilisation in displays, actuators and memory components. In this study, diffraction techniques were employed to study the structural changes accompanying the temperature increase and the light irradiation of a defect [2 × 2] triiron(ii) metallogrid of the form [Fe(II)(3)L(H)(2)(HL(H))(2)](BF(4))(4)·4MeCN (FE3), L(H) = 3,5-bis{6-(2,2′-bipyridyl)}pyrazole. Although a multi-temperature crystallographic investigation on single crystals evidenced that the compound does not exhibit a thermal spin transition, the structural analysis of the defect grid suggests that the flexibility of the grid, provided by a metal-devoid vertex, leads to interesting characteristics that can be used for intermolecular cooperativity in related thermally responsive systems. Time-resolved photocrystallography results reveal that upon excitation with a ps laser pulse, the defect grid shows the first two steps of the out-of-equilibrium process, namely the photoinduced and elastic steps, occurring at the ps and ns time scales, respectively. Similar to a previously reported [2 × 2] tetrairon(ii) metallogrid, FE3 exhibits a local distortion of the entire grid during the photoinduced step and a long-range distortion of the lattice during the elastic step. Although the lifetime of the pure photoinduced high spin (HS) state is longer in the tetranuclear grid than in the defect grid, suggesting that the global nuclearity plays a crucial role for the lifetime of the photoinduced species, the influence of the co-crystalising solvent on the lifetime of the photoinduced HS state remains unknown. This study sheds light on the out-of-equilibrium dynamics of a thermally silent defect triiron SCO metallogrid. The Royal Society of Chemistry 2023-09-01 /pmc/articles/PMC10498823/ /pubmed/37656445 http://dx.doi.org/10.1039/d3dt02067c Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Velazquez-Garcia, Jose de Jesus Basuroy, Krishnayan Storozhuk, Darina Wong, Joanne Demeshko, Serhiy Meyer, Franc Henning, Robert Techert, Simone Structural dynamics of a thermally silent triiron(ii) spin crossover defect grid complex |
title | Structural dynamics of a thermally silent triiron(ii) spin crossover defect grid complex |
title_full | Structural dynamics of a thermally silent triiron(ii) spin crossover defect grid complex |
title_fullStr | Structural dynamics of a thermally silent triiron(ii) spin crossover defect grid complex |
title_full_unstemmed | Structural dynamics of a thermally silent triiron(ii) spin crossover defect grid complex |
title_short | Structural dynamics of a thermally silent triiron(ii) spin crossover defect grid complex |
title_sort | structural dynamics of a thermally silent triiron(ii) spin crossover defect grid complex |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10498823/ https://www.ncbi.nlm.nih.gov/pubmed/37656445 http://dx.doi.org/10.1039/d3dt02067c |
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