Guest induced reversible on-off switching of elastic frustration in a 3D spin crossover coordination polymer with room temperature hysteretic behaviour

Lucía Piñeiro-López; Francisco Javier Valverde-Muñoz; Elzbieta Trzop; M. Carmen Muñoz; Maksym Seredyuk; Javier Castells-Gil; Iván da Silva; Carlos Martí-Gastaldo; Eric Collet; José Antonio Real

doi:10.1039/d0sc04420b

Guest induced reversible on-off switching of elastic frustration in a 3D spin crossover coordination polymer with room temperature hysteretic behaviour

Lucía Piñeiro-López
, Francisco Javier Valverde-Muñoz
, Elzbieta Trzop
, M. Carmen Muñoz
, Maksym Seredyuk
, Javier Castells-Gil
, Iván da Silva
, Carlos Martí-Gastaldo
, Eric Collet^*
, José Antonio Real^*

^*Corresponding author for this work

Chemistry

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

Abstract

A binary reversible switch between low-temperature multi-step spin crossover (SCO), through the evolution of the populationγ_HS(T) with high-spin (HS)-low-spin (LS) sequence: HS₁LS₀(state 1) ↔ HS_2/3LS_1/3(state 2) ↔ HS_1/2LS_1/2(state 3) ↔ HS_1/3LS_2/3(state 4) ↔ HS₀LS₁(state 5), and complete one step hysteretic spin transition featuring 20 K wide thermal hysteresis centred at 290 K occurs in the three-dimensional (3D) Hofmann-type porous coordination polymer {Fe^II(3,8phen)[Au(CN)₂]₂}·xPhNO₂(3,8phen = 3,8-phenanthroline, PhNO₂= nitrobenzene), made up of two identical interpenetrated pcu-type frameworks. The included PhNO₂guest (x= 1,1·PhNO₂) acts as a molecular wedge between the interpenetrated 3D frameworksviaPhNO₂-3,8phen intermolecular recognition and is the source of the strong elastic frustration responsible for the multi-step regime. Detailed X-ray single crystal analysis reflects competition between spatial periodicities of structurally inequivalent HS and LS SCO centres featuring: (i) symmetry breaking (state 3) with ⋯HS-LS⋯ ordering withγ_HS= 1/2; and (ii) occurrence of spatial modulation of the structure providing evidence for stabilization of local or aperiodic ordered mixed spin states for states 2 and 4 (withγ_HS≈ 2/3) and 4 (withγ_HS≈ 1/3), respectively. Belowc.a.20 K, structural and magnetic analyses show the photogeneration of a metastable HS*, state 6. The room-temperature single-step hysteretic regime appears with release of the guest (x= 0,1) and the elastic frustration, and reversibly switches back to the original four-step behaviour upon guest re-adsorption. Both uncommon relevant SCO events meeting in the same material represent a rare opportunity to compare them in the frame of antiferro- and ferro-elastic transitions.

Original language	English
Pages (from-to)	1317-1326
Number of pages	10
Journal	Chemical Science
Volume	12
Issue number	4
Early online date	23 Nov 2020
DOIs	https://doi.org/10.1039/d0sc04420b
Publication status	Published - 28 Jan 2021

Bibliographical note

Publisher Copyright:
© The Royal Society of Chemistry 2020.

ASJC Scopus subject areas

General Chemistry

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Cite this

Piñeiro-López, L., Valverde-Muñoz, F. J., Trzop, E., Muñoz, M. C., Seredyuk, M., Castells-Gil, J., da Silva, I., Martí-Gastaldo, C., Collet, E., & Real, J. A. (2021). Guest induced reversible on-off switching of elastic frustration in a 3D spin crossover coordination polymer with room temperature hysteretic behaviour. Chemical Science, 12(4), 1317-1326. https://doi.org/10.1039/d0sc04420b

@article{87d16da09207416bad895236f3dfe96a,

title = "Guest induced reversible on-off switching of elastic frustration in a 3D spin crossover coordination polymer with room temperature hysteretic behaviour",

abstract = "A binary reversible switch between low-temperature multi-step spin crossover (SCO), through the evolution of the populationγHS(T) with high-spin (HS)-low-spin (LS) sequence: HS1LS0(state 1) ↔ HS2/3LS1/3(state 2) ↔ HS1/2LS1/2(state 3) ↔ HS1/3LS2/3(state 4) ↔ HS0LS1(state 5), and complete one step hysteretic spin transition featuring 20 K wide thermal hysteresis centred at 290 K occurs in the three-dimensional (3D) Hofmann-type porous coordination polymer \{FeII(3,8phen)[Au(CN)2]2\}·xPhNO2(3,8phen = 3,8-phenanthroline, PhNO2= nitrobenzene), made up of two identical interpenetrated pcu-type frameworks. The included PhNO2guest (x= 1,1·PhNO2) acts as a molecular wedge between the interpenetrated 3D frameworksviaPhNO2-3,8phen intermolecular recognition and is the source of the strong elastic frustration responsible for the multi-step regime. Detailed X-ray single crystal analysis reflects competition between spatial periodicities of structurally inequivalent HS and LS SCO centres featuring: (i) symmetry breaking (state 3) with ⋯HS-LS⋯ ordering withγHS= 1/2; and (ii) occurrence of spatial modulation of the structure providing evidence for stabilization of local or aperiodic ordered mixed spin states for states 2 and 4 (withγHS≈ 2/3) and 4 (withγHS≈ 1/3), respectively. Belowc.a.20 K, structural and magnetic analyses show the photogeneration of a metastable HS*, state 6. The room-temperature single-step hysteretic regime appears with release of the guest (x= 0,1) and the elastic frustration, and reversibly switches back to the original four-step behaviour upon guest re-adsorption. Both uncommon relevant SCO events meeting in the same material represent a rare opportunity to compare them in the frame of antiferro- and ferro-elastic transitions.",

author = "Luc{\'i}a Pi{\~n}eiro-L{\'o}pez and Valverde-Mu{\~n}oz, \{Francisco Javier\} and Elzbieta Trzop and Mu{\~n}oz, \{M. Carmen\} and Maksym Seredyuk and Javier Castells-Gil and \{da Silva\}, Iv{\'a}n and Carlos Mart{\'i}-Gastaldo and Eric Collet and Real, \{Jos{\'e} Antonio\}",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2020.",

year = "2021",

month = jan,

day = "28",

doi = "10.1039/d0sc04420b",

language = "English",

volume = "12",

pages = "1317--1326",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "4",

}

Piñeiro-López, L, Valverde-Muñoz, FJ, Trzop, E, Muñoz, MC, Seredyuk, M, Castells-Gil, J, da Silva, I, Martí-Gastaldo, C, Collet, E & Real, JA 2021, 'Guest induced reversible on-off switching of elastic frustration in a 3D spin crossover coordination polymer with room temperature hysteretic behaviour', Chemical Science, vol. 12, no. 4, pp. 1317-1326. https://doi.org/10.1039/d0sc04420b

TY - JOUR

T1 - Guest induced reversible on-off switching of elastic frustration in a 3D spin crossover coordination polymer with room temperature hysteretic behaviour

AU - Piñeiro-López, Lucía

AU - Valverde-Muñoz, Francisco Javier

AU - Trzop, Elzbieta

AU - Muñoz, M. Carmen

AU - Seredyuk, Maksym

AU - Castells-Gil, Javier

AU - da Silva, Iván

AU - Martí-Gastaldo, Carlos

AU - Collet, Eric

AU - Real, José Antonio

PY - 2021/1/28

Y1 - 2021/1/28

N2 - A binary reversible switch between low-temperature multi-step spin crossover (SCO), through the evolution of the populationγHS(T) with high-spin (HS)-low-spin (LS) sequence: HS1LS0(state 1) ↔ HS2/3LS1/3(state 2) ↔ HS1/2LS1/2(state 3) ↔ HS1/3LS2/3(state 4) ↔ HS0LS1(state 5), and complete one step hysteretic spin transition featuring 20 K wide thermal hysteresis centred at 290 K occurs in the three-dimensional (3D) Hofmann-type porous coordination polymer {FeII(3,8phen)[Au(CN)2]2}·xPhNO2(3,8phen = 3,8-phenanthroline, PhNO2= nitrobenzene), made up of two identical interpenetrated pcu-type frameworks. The included PhNO2guest (x= 1,1·PhNO2) acts as a molecular wedge between the interpenetrated 3D frameworksviaPhNO2-3,8phen intermolecular recognition and is the source of the strong elastic frustration responsible for the multi-step regime. Detailed X-ray single crystal analysis reflects competition between spatial periodicities of structurally inequivalent HS and LS SCO centres featuring: (i) symmetry breaking (state 3) with ⋯HS-LS⋯ ordering withγHS= 1/2; and (ii) occurrence of spatial modulation of the structure providing evidence for stabilization of local or aperiodic ordered mixed spin states for states 2 and 4 (withγHS≈ 2/3) and 4 (withγHS≈ 1/3), respectively. Belowc.a.20 K, structural and magnetic analyses show the photogeneration of a metastable HS*, state 6. The room-temperature single-step hysteretic regime appears with release of the guest (x= 0,1) and the elastic frustration, and reversibly switches back to the original four-step behaviour upon guest re-adsorption. Both uncommon relevant SCO events meeting in the same material represent a rare opportunity to compare them in the frame of antiferro- and ferro-elastic transitions.

AB - A binary reversible switch between low-temperature multi-step spin crossover (SCO), through the evolution of the populationγHS(T) with high-spin (HS)-low-spin (LS) sequence: HS1LS0(state 1) ↔ HS2/3LS1/3(state 2) ↔ HS1/2LS1/2(state 3) ↔ HS1/3LS2/3(state 4) ↔ HS0LS1(state 5), and complete one step hysteretic spin transition featuring 20 K wide thermal hysteresis centred at 290 K occurs in the three-dimensional (3D) Hofmann-type porous coordination polymer {FeII(3,8phen)[Au(CN)2]2}·xPhNO2(3,8phen = 3,8-phenanthroline, PhNO2= nitrobenzene), made up of two identical interpenetrated pcu-type frameworks. The included PhNO2guest (x= 1,1·PhNO2) acts as a molecular wedge between the interpenetrated 3D frameworksviaPhNO2-3,8phen intermolecular recognition and is the source of the strong elastic frustration responsible for the multi-step regime. Detailed X-ray single crystal analysis reflects competition between spatial periodicities of structurally inequivalent HS and LS SCO centres featuring: (i) symmetry breaking (state 3) with ⋯HS-LS⋯ ordering withγHS= 1/2; and (ii) occurrence of spatial modulation of the structure providing evidence for stabilization of local or aperiodic ordered mixed spin states for states 2 and 4 (withγHS≈ 2/3) and 4 (withγHS≈ 1/3), respectively. Belowc.a.20 K, structural and magnetic analyses show the photogeneration of a metastable HS*, state 6. The room-temperature single-step hysteretic regime appears with release of the guest (x= 0,1) and the elastic frustration, and reversibly switches back to the original four-step behaviour upon guest re-adsorption. Both uncommon relevant SCO events meeting in the same material represent a rare opportunity to compare them in the frame of antiferro- and ferro-elastic transitions.

UR - https://www.scopus.com/pages/publications/85100494802

U2 - 10.1039/d0sc04420b

DO - 10.1039/d0sc04420b

M3 - Article

AN - SCOPUS:85100494802

SN - 2041-6520

VL - 12

SP - 1317

EP - 1326

JO - Chemical Science

JF - Chemical Science

IS - 4

ER -

Guest induced reversible on-off switching of elastic frustration in a 3D spin crossover coordination polymer with room temperature hysteretic behaviour

Abstract

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