First step towards a Devil's Staircase in Spin Crossover materials First step towards Devil's Staircase in Spin Crossover materials

The unprecedented bimetallic 2D coordination polymer {Fe[(Hg(SCN)3 )2 ](4,4'-bipy)2 }n exhibits a thermal high-spin (HS)↔low-spin (LS) staircase-like conversion characterized by a multi-step dependence of the HS molar fraction γHS . Between the fully HS (γHS =1) and LS (γHS =0) phases, two step...

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Veröffentlicht in:Angewandte Chemie International Edition 2016-05, Vol.55 (30), p.8675-8679
Hauptverfasser: Trzop, Elzbieta, Zhang, Daopeng, Piñeiro-Lopez, Lucia, Valverde-Muñoz, Francisco J., Carmen Muñoz, M, Palatinus, Lukáš, Guérin, Laurent, Cailleau, Hervé, Real, José Antonio, Collet, Eric
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container_issue 30
container_start_page 8675
container_title Angewandte Chemie International Edition
container_volume 55
creator Trzop, Elzbieta
Zhang, Daopeng
Piñeiro-Lopez, Lucia
Valverde-Muñoz, Francisco J.
Carmen Muñoz, M
Palatinus, Lukáš
Guérin, Laurent
Cailleau, Hervé
Real, José Antonio
Collet, Eric
description The unprecedented bimetallic 2D coordination polymer {Fe[(Hg(SCN)3 )2 ](4,4'-bipy)2 }n exhibits a thermal high-spin (HS)↔low-spin (LS) staircase-like conversion characterized by a multi-step dependence of the HS molar fraction γHS . Between the fully HS (γHS =1) and LS (γHS =0) phases, two steps associated with different ordering appear in terms of spin-state concentration waves (SSCW). On the γHS ≈0.5 step, a periodic SSCW forms with a HS-LS-HS-LS sequence. On the γHS ≈0.34 step, the 4D superspace crystallography structural refinement reveals an aperiodic SSCW, with a HS-LS sequence incommensurate with the molecular lattice. The formation of these different long-range spatially ordered structures of LS and HS states during the multi-step spin-crossover is discussed within the framework of "Devil's staircase"-type transitions. Spatially modulated phases are known in various types of materials but are uniquely related to molecular HS/LS bistability in this case.
doi_str_mv 10.1002/anie.201602441
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Between the fully HS (γHS =1) and LS (γHS =0) phases, two steps associated with different ordering appear in terms of spin-state concentration waves (SSCW). On the γHS ≈0.5 step, a periodic SSCW forms with a HS-LS-HS-LS sequence. On the γHS ≈0.34 step, the 4D superspace crystallography structural refinement reveals an aperiodic SSCW, with a HS-LS sequence incommensurate with the molecular lattice. The formation of these different long-range spatially ordered structures of LS and HS states during the multi-step spin-crossover is discussed within the framework of "Devil's staircase"-type transitions. 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Condensed Matter
Coordination chemistry
Cristallography
Materials Science
Physics
title First step towards a Devil's Staircase in Spin Crossover materials First step towards Devil's Staircase in Spin Crossover materials
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