[Fe(μ-btzmp)2(btzmp)2](ClO4)2: a doubly-bridged 1D spin-transition bistetrazole-based polymer showing thermal hysteresis behaviour

Manuel Quesada, Huub Kooijman, Patrick Gamez, José Sánchez Costa, Petra J. van Koningsbruggen, Peter Weinberger, Michael Reissner, Anthony L. Spek, Jaap G. Haasnoot, Jan Reedijk

Research output: Contribution to journalArticle

Abstract

The reaction of btzmp (1,2-bis(tetrazol-1-yl)-2-methylpropane) with Fe(ClO4)2 generates a 1D polymeric species, [Fe(μ-btzmp)2(btzmp)2](ClO4)2, showing a steep spin transition (T½↑ = 136 K and T ½↓ = 133 K) with a 3 K thermal hysteresis. The crystal structure at 100 and 200 K reveals that, in contrast to other bistetrazole based spin-transition systems such as [Fe(endi)3](BF4)2 and [Fe(btzp)3](ClO4)2, the present compound has only two ligands bridging the metallic centres, while the other two coordination positions are occupied by two mono-coordinated (non-bridging) btzmp ligands. This peculiarity confers an unprecedented crystal packing in the series of 1D bistetrazole based polymers. The change in spin state is accompanied by an order/disorder transition of the ClO4- counterion. A careful examination of the structural changes occurring upon the spin transition indicates that this order/disorder is most likely affected by the modification of the [tetrazole-centroid]-ND-Fe angle (which is typical of bistetrazole spin-transition materials). Apart from X-ray analysis, also magnetic susceptibility, Mössbauer and UV-vis spectroscopies have been used to characterise the HS and the LS states of [Fe(µ-btzmp)2(btzmp)2](ClO4)2.

Original languageEnglish
Pages (from-to)5434-5440
Number of pages7
JournalDalton Transactions
Issue number46
Early online date4 Oct 2007
DOIs
Publication statusPublished - 4 Oct 2007

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Hysteresis
Polymers
Order disorder transitions
Ligands
X ray analysis
Ultraviolet spectroscopy
Magnetic susceptibility
Crystal structure
Hot Temperature
perchlorate
Crystals

Keywords

  • ClO4
  • bistetrazole
  • thermal hysteresis
  • spin-transition

Cite this

Quesada, Manuel ; Kooijman, Huub ; Gamez, Patrick ; Sánchez Costa, José ; van Koningsbruggen, Petra J. ; Weinberger, Peter ; Reissner, Michael ; Spek, Anthony L. ; Haasnoot, Jaap G. ; Reedijk, Jan. / [Fe(μ-btzmp)2(btzmp)2](ClO4)2 : a doubly-bridged 1D spin-transition bistetrazole-based polymer showing thermal hysteresis behaviour. In: Dalton Transactions. 2007 ; No. 46. pp. 5434-5440.
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title = "[Fe(μ-btzmp)2(btzmp)2](ClO4)2: a doubly-bridged 1D spin-transition bistetrazole-based polymer showing thermal hysteresis behaviour",
abstract = "The reaction of btzmp (1,2-bis(tetrazol-1-yl)-2-methylpropane) with Fe(ClO4)2 generates a 1D polymeric species, [Fe(μ-btzmp)2(btzmp)2](ClO4)2, showing a steep spin transition (T½↑ = 136 K and T ½↓ = 133 K) with a 3 K thermal hysteresis. The crystal structure at 100 and 200 K reveals that, in contrast to other bistetrazole based spin-transition systems such as [Fe(endi)3](BF4)2 and [Fe(btzp)3](ClO4)2, the present compound has only two ligands bridging the metallic centres, while the other two coordination positions are occupied by two mono-coordinated (non-bridging) btzmp ligands. This peculiarity confers an unprecedented crystal packing in the series of 1D bistetrazole based polymers. The change in spin state is accompanied by an order/disorder transition of the ClO4- counterion. A careful examination of the structural changes occurring upon the spin transition indicates that this order/disorder is most likely affected by the modification of the [tetrazole-centroid]-ND-Fe angle (which is typical of bistetrazole spin-transition materials). Apart from X-ray analysis, also magnetic susceptibility, M{\"o}ssbauer and UV-vis spectroscopies have been used to characterise the HS and the LS states of [Fe(µ-btzmp)2(btzmp)2](ClO4)2.",
keywords = "ClO4, bistetrazole, thermal hysteresis, spin-transition",
author = "Manuel Quesada and Huub Kooijman and Patrick Gamez and {S{\'a}nchez Costa}, Jos{\'e} and {van Koningsbruggen}, {Petra J.} and Peter Weinberger and Michael Reissner and Spek, {Anthony L.} and Haasnoot, {Jaap G.} and Jan Reedijk",
note = "Copyright 2008 Elsevier B.V., All rights reserved.",
year = "2007",
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doi = "10.1039/b709460d",
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Quesada, M, Kooijman, H, Gamez, P, Sánchez Costa, J, van Koningsbruggen, PJ, Weinberger, P, Reissner, M, Spek, AL, Haasnoot, JG & Reedijk, J 2007, '[Fe(μ-btzmp)2(btzmp)2](ClO4)2: a doubly-bridged 1D spin-transition bistetrazole-based polymer showing thermal hysteresis behaviour', Dalton Transactions, no. 46, pp. 5434-5440. https://doi.org/10.1039/b709460d

[Fe(μ-btzmp)2(btzmp)2](ClO4)2 : a doubly-bridged 1D spin-transition bistetrazole-based polymer showing thermal hysteresis behaviour. / Quesada, Manuel; Kooijman, Huub; Gamez, Patrick; Sánchez Costa, José; van Koningsbruggen, Petra J.; Weinberger, Peter; Reissner, Michael; Spek, Anthony L.; Haasnoot, Jaap G.; Reedijk, Jan.

In: Dalton Transactions, No. 46, 04.10.2007, p. 5434-5440.

Research output: Contribution to journalArticle

TY - JOUR

T1 - [Fe(μ-btzmp)2(btzmp)2](ClO4)2

T2 - a doubly-bridged 1D spin-transition bistetrazole-based polymer showing thermal hysteresis behaviour

AU - Quesada, Manuel

AU - Kooijman, Huub

AU - Gamez, Patrick

AU - Sánchez Costa, José

AU - van Koningsbruggen, Petra J.

AU - Weinberger, Peter

AU - Reissner, Michael

AU - Spek, Anthony L.

AU - Haasnoot, Jaap G.

AU - Reedijk, Jan

N1 - Copyright 2008 Elsevier B.V., All rights reserved.

PY - 2007/10/4

Y1 - 2007/10/4

N2 - The reaction of btzmp (1,2-bis(tetrazol-1-yl)-2-methylpropane) with Fe(ClO4)2 generates a 1D polymeric species, [Fe(μ-btzmp)2(btzmp)2](ClO4)2, showing a steep spin transition (T½↑ = 136 K and T ½↓ = 133 K) with a 3 K thermal hysteresis. The crystal structure at 100 and 200 K reveals that, in contrast to other bistetrazole based spin-transition systems such as [Fe(endi)3](BF4)2 and [Fe(btzp)3](ClO4)2, the present compound has only two ligands bridging the metallic centres, while the other two coordination positions are occupied by two mono-coordinated (non-bridging) btzmp ligands. This peculiarity confers an unprecedented crystal packing in the series of 1D bistetrazole based polymers. The change in spin state is accompanied by an order/disorder transition of the ClO4- counterion. A careful examination of the structural changes occurring upon the spin transition indicates that this order/disorder is most likely affected by the modification of the [tetrazole-centroid]-ND-Fe angle (which is typical of bistetrazole spin-transition materials). Apart from X-ray analysis, also magnetic susceptibility, Mössbauer and UV-vis spectroscopies have been used to characterise the HS and the LS states of [Fe(µ-btzmp)2(btzmp)2](ClO4)2.

AB - The reaction of btzmp (1,2-bis(tetrazol-1-yl)-2-methylpropane) with Fe(ClO4)2 generates a 1D polymeric species, [Fe(μ-btzmp)2(btzmp)2](ClO4)2, showing a steep spin transition (T½↑ = 136 K and T ½↓ = 133 K) with a 3 K thermal hysteresis. The crystal structure at 100 and 200 K reveals that, in contrast to other bistetrazole based spin-transition systems such as [Fe(endi)3](BF4)2 and [Fe(btzp)3](ClO4)2, the present compound has only two ligands bridging the metallic centres, while the other two coordination positions are occupied by two mono-coordinated (non-bridging) btzmp ligands. This peculiarity confers an unprecedented crystal packing in the series of 1D bistetrazole based polymers. The change in spin state is accompanied by an order/disorder transition of the ClO4- counterion. A careful examination of the structural changes occurring upon the spin transition indicates that this order/disorder is most likely affected by the modification of the [tetrazole-centroid]-ND-Fe angle (which is typical of bistetrazole spin-transition materials). Apart from X-ray analysis, also magnetic susceptibility, Mössbauer and UV-vis spectroscopies have been used to characterise the HS and the LS states of [Fe(µ-btzmp)2(btzmp)2](ClO4)2.

KW - ClO4

KW - bistetrazole

KW - thermal hysteresis

KW - spin-transition

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U2 - 10.1039/b709460d

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