Multimetastability in a spin-crossover compound leading to different high-spin-to-low-spin relaxation dynamics

Gavin A. Craig, Jose Sánchez Costa, Simon J. Teat, Olivier Roubeau, Dmitry S. Yufit, Judith. A. K. Howard, Guillem Aromí

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The relaxation kinetics of both the thermally trapped and photoinduced high-spin (HS) states of the spin-crossover compound [Fe(H4L)2](ClO4)2·H2O·2(CH3)2CO (1) were measured and found to differ significantly. Calorimetry measurements then demonstrated that relaxation of the thermally trapped phase was concurrent with two separate processes, not previously detected as such. Determination of the photogenerated HS structure revealed a new metastable HS state of the system, much closer structurally to the low-spin phase than the thermally trapped one. This difference is proposed as the root of the disparate kinetic behavior, which is proposed to require two processes in the case of the structurally more complex thermally trapped state. Therefore, light irradiation is shown as a mechanism to decouple effectively the structural and magnetic phase transitions that occur in 1 during the course of its spin crossover.
LanguageEnglish
Pages7203-7209
Number of pages7
JournalInorganic Chemistry
Volume52
Issue number12
DOIs
Publication statusPublished - 17 Jun 2013

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crossovers
Kinetics
Calorimetry
Phase transitions
Irradiation
kinetics
heat measurement
irradiation
perchlorate

Keywords

  • multimetastability
  • spin-crossover compound
  • relaxation kinetics

Cite this

Craig, G. A., Costa, J. S., Teat, S. J., Roubeau, O., Yufit, D. S., Howard, J. A. K., & Aromí, G. (2013). Multimetastability in a spin-crossover compound leading to different high-spin-to-low-spin relaxation dynamics. Inorganic Chemistry, 52(12), 7203-7209. https://doi.org/10.1021/ic400776x
Craig, Gavin A. ; Costa, Jose Sánchez ; Teat, Simon J. ; Roubeau, Olivier ; Yufit, Dmitry S. ; Howard, Judith. A. K. ; Aromí, Guillem. / Multimetastability in a spin-crossover compound leading to different high-spin-to-low-spin relaxation dynamics. In: Inorganic Chemistry. 2013 ; Vol. 52, No. 12. pp. 7203-7209.
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Multimetastability in a spin-crossover compound leading to different high-spin-to-low-spin relaxation dynamics. / Craig, Gavin A.; Costa, Jose Sánchez; Teat, Simon J.; Roubeau, Olivier; Yufit, Dmitry S.; Howard, Judith. A. K.; Aromí, Guillem.

In: Inorganic Chemistry, Vol. 52, No. 12, 17.06.2013, p. 7203-7209.

Research output: Contribution to journalArticle

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T1 - Multimetastability in a spin-crossover compound leading to different high-spin-to-low-spin relaxation dynamics

AU - Craig, Gavin A.

AU - Costa, Jose Sánchez

AU - Teat, Simon J.

AU - Roubeau, Olivier

AU - Yufit, Dmitry S.

AU - Howard, Judith. A. K.

AU - Aromí, Guillem

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AB - The relaxation kinetics of both the thermally trapped and photoinduced high-spin (HS) states of the spin-crossover compound [Fe(H4L)2](ClO4)2·H2O·2(CH3)2CO (1) were measured and found to differ significantly. Calorimetry measurements then demonstrated that relaxation of the thermally trapped phase was concurrent with two separate processes, not previously detected as such. Determination of the photogenerated HS structure revealed a new metastable HS state of the system, much closer structurally to the low-spin phase than the thermally trapped one. This difference is proposed as the root of the disparate kinetic behavior, which is proposed to require two processes in the case of the structurally more complex thermally trapped state. Therefore, light irradiation is shown as a mechanism to decouple effectively the structural and magnetic phase transitions that occur in 1 during the course of its spin crossover.

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