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Reversible Guest Binding in a Non-Porous FeII Coordination Polymer Host Toggles Spin Crossover

Journal article
Authors Anders Lennartson
P. Southon
N. F. Sciortino
C. J. Kepert
C. Frandsen
S. Mørup
S. Piligkos
C. J. McKenzie
Published in Chemistry - A European Journal
Volume 21
Issue 45
Pages 16066-16072
ISSN 0947-6539
Publisher Wiley-VCH Verlag
Publication year 2015
Published at
Pages 16066-16072
Language en
Keywords coordination polymers, host-guest systems, iron, sorption, spin crossover
Subject categories Polymer Technologies

Abstract

Formation of either a dimetallic compound or a 1D coordination polymer of adiponitrile adducts of [Fe(bpte)]2+ (bpte=[1,2-bis(pyridin-2-ylmethyl)thio]ethane) can be controlled by the choice of counteranion. The iron(II) atoms of the bis(adiponitrile)-bridged dimeric complex [Fe2(bpte)2(μ2-(NC(CH2)4CN)2](SbF6)4 (2) are low spin at room temperature, as are those in the polymeric adiponitrile-linked acetone solvate polymer {[Fe(bpte)(μ2-NC(CH2)4CN)](BPh4)2 Me2CO} (3Me2CO). On heating 3Me2CO to 80°C, the acetone is abruptly removed with an accompanying purple to dull lavender colour change corresponding to a conversion to a high-spin compound. Cooling reveals that the desolvate 3 shows hysteretic and abrupt spin crossover (SCO) S=0虠S=2 behaviour centred at 205K. Non-porous 3 can reversibly absorb one equivalent of acetone per iron centre to regenerate the same crystalline phase of 3Me2CO concurrently reinstating a low-spin state.

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