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Light-Induced Spin State Switching and Relaxation in Spin Pairs of Copper(II)-Nitroxide Based Molecular Magnets. / Tumanov, Sergey V.; Veber, Sergey L.; Tolstikov, Svyatoslav E. et al.

In: Inorganic Chemistry, Vol. 56, No. 19, 02.10.2017, p. 11729-11737.

Research output: Contribution to journal › Article › peer-review

Harvard

Tumanov, SV, Veber, SL, Tolstikov, SE, Artiukhova, NA, Romanenko, GV, Ovcharenko, VI & Fedin, MV 2017, 'Light-Induced Spin State Switching and Relaxation in Spin Pairs of Copper(II)-Nitroxide Based Molecular Magnets', Inorganic Chemistry, vol. 56, no. 19, pp. 11729-11737. https://doi.org/10.1021/acs.inorgchem.7b01689

APA

Tumanov, S. V., Veber, S. L., Tolstikov, S. E., Artiukhova, N. A., Romanenko, G. V., Ovcharenko, V. I., & Fedin, M. V. (2017). Light-Induced Spin State Switching and Relaxation in Spin Pairs of Copper(II)-Nitroxide Based Molecular Magnets. Inorganic Chemistry, 56(19), 11729-11737. https://doi.org/10.1021/acs.inorgchem.7b01689

Vancouver

Tumanov SV, Veber SL, Tolstikov SE, Artiukhova NA, Romanenko GV, Ovcharenko VI et al. Light-Induced Spin State Switching and Relaxation in Spin Pairs of Copper(II)-Nitroxide Based Molecular Magnets. Inorganic Chemistry. 2017 Oct 2;56(19):11729-11737. doi: 10.1021/acs.inorgchem.7b01689

Author

Tumanov, Sergey V. ; Veber, Sergey L. ; Tolstikov, Svyatoslav E. et al. / Light-Induced Spin State Switching and Relaxation in Spin Pairs of Copper(II)-Nitroxide Based Molecular Magnets. In: Inorganic Chemistry. 2017 ; Vol. 56, No. 19. pp. 11729-11737.

BibTeX

@article{4d6628adf5094d4b92ccb54ae0635d64,
title = "Light-Induced Spin State Switching and Relaxation in Spin Pairs of Copper(II)-Nitroxide Based Molecular Magnets",
abstract = "Similar to spin-crossover (SCO) compounds, spin states of copper(II)-nitroxide based molecular magnets can be switched by various external stimuli including temperature and light. Although photoswitching and reverse relaxation of nitroxide-copper(II)-nitroxide triads were investigated in some detail, similar study for copper(II)-nitroxide spin pairs was still missing. In this work we address photoswitching and relaxation phenomena in exchange-coupled spin pairs of this family of molecular magnets. Using electron paramagnetic resonance (EPR) spectroscopy with photoexcitation, we demonstrate that compared to triad-containing compounds the photoinduced weakly coupled spin (WS) states of copper(II)-nitroxide pairs are remarkably more stable at cryogenic temperatures and relax to the ground strongly coupled spin (SS) states on the scale of days. The structural changes between SS and WS states, e.g., differences in Cu-Onitroxide distances, are much more pronounced for spin pairs than for spin triads in most of the studied copper(II)-nitroxide based molecular magnets. This results in higher energy barrier between WS and SS states of spin pairs and governs higher stability of their photoinduced WS states. Therefore, the longer-lived photoinduced states in copper(II)-nitroxide molecular magnets should be searched within the compounds experiencing largest structural changes upon thermal spin transition. This advancement in understanding of LIESST-like phenomena in copper(II)-nitroxide molecular magnets allows us to propose them as interesting playgrounds for benchmarking the basic factors governing the stability of photoinduced states in other SCO and SCO-like photoswitchable systems.",
author = "Tumanov, {Sergey V.} and Veber, {Sergey L.} and Tolstikov, {Svyatoslav E.} and Artiukhova, {Natalia A.} and Romanenko, {Galina V.} and Ovcharenko, {Victor I.} and Fedin, {Matvey V.}",
note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",
year = "2017",
month = oct,
day = "2",
doi = "10.1021/acs.inorgchem.7b01689",
language = "English",
volume = "56",
pages = "11729--11737",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "19",

}

RIS

TY - JOUR

T1 - Light-Induced Spin State Switching and Relaxation in Spin Pairs of Copper(II)-Nitroxide Based Molecular Magnets

AU - Tumanov, Sergey V.

AU - Veber, Sergey L.

AU - Tolstikov, Svyatoslav E.

AU - Artiukhova, Natalia A.

AU - Romanenko, Galina V.

AU - Ovcharenko, Victor I.

AU - Fedin, Matvey V.

N1 - Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/10/2

Y1 - 2017/10/2

N2 - Similar to spin-crossover (SCO) compounds, spin states of copper(II)-nitroxide based molecular magnets can be switched by various external stimuli including temperature and light. Although photoswitching and reverse relaxation of nitroxide-copper(II)-nitroxide triads were investigated in some detail, similar study for copper(II)-nitroxide spin pairs was still missing. In this work we address photoswitching and relaxation phenomena in exchange-coupled spin pairs of this family of molecular magnets. Using electron paramagnetic resonance (EPR) spectroscopy with photoexcitation, we demonstrate that compared to triad-containing compounds the photoinduced weakly coupled spin (WS) states of copper(II)-nitroxide pairs are remarkably more stable at cryogenic temperatures and relax to the ground strongly coupled spin (SS) states on the scale of days. The structural changes between SS and WS states, e.g., differences in Cu-Onitroxide distances, are much more pronounced for spin pairs than for spin triads in most of the studied copper(II)-nitroxide based molecular magnets. This results in higher energy barrier between WS and SS states of spin pairs and governs higher stability of their photoinduced WS states. Therefore, the longer-lived photoinduced states in copper(II)-nitroxide molecular magnets should be searched within the compounds experiencing largest structural changes upon thermal spin transition. This advancement in understanding of LIESST-like phenomena in copper(II)-nitroxide molecular magnets allows us to propose them as interesting playgrounds for benchmarking the basic factors governing the stability of photoinduced states in other SCO and SCO-like photoswitchable systems.

AB - Similar to spin-crossover (SCO) compounds, spin states of copper(II)-nitroxide based molecular magnets can be switched by various external stimuli including temperature and light. Although photoswitching and reverse relaxation of nitroxide-copper(II)-nitroxide triads were investigated in some detail, similar study for copper(II)-nitroxide spin pairs was still missing. In this work we address photoswitching and relaxation phenomena in exchange-coupled spin pairs of this family of molecular magnets. Using electron paramagnetic resonance (EPR) spectroscopy with photoexcitation, we demonstrate that compared to triad-containing compounds the photoinduced weakly coupled spin (WS) states of copper(II)-nitroxide pairs are remarkably more stable at cryogenic temperatures and relax to the ground strongly coupled spin (SS) states on the scale of days. The structural changes between SS and WS states, e.g., differences in Cu-Onitroxide distances, are much more pronounced for spin pairs than for spin triads in most of the studied copper(II)-nitroxide based molecular magnets. This results in higher energy barrier between WS and SS states of spin pairs and governs higher stability of their photoinduced WS states. Therefore, the longer-lived photoinduced states in copper(II)-nitroxide molecular magnets should be searched within the compounds experiencing largest structural changes upon thermal spin transition. This advancement in understanding of LIESST-like phenomena in copper(II)-nitroxide molecular magnets allows us to propose them as interesting playgrounds for benchmarking the basic factors governing the stability of photoinduced states in other SCO and SCO-like photoswitchable systems.

UR - http://www.scopus.com/inward/record.url?scp=85030551048&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.7b01689

DO - 10.1021/acs.inorgchem.7b01689

M3 - Article

C2 - 28933835

AN - SCOPUS:85030551048

VL - 56

SP - 11729

EP - 11737

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 19

ER -

ID: 9894184