Issue 24, 2020

Enhanced dielectricity coupled to spin-crossover in a one-dimensional polymer iron(ii) incorporating tetrathiafulvalene

Abstract

In designing multifunctional materials for potential switches that can be used as memory devices, the high-spin (HS) to low-spin (LS) crossover (SCO) one-dimensional polymer, [FeII(L)(4,4′-bpy)]n, was constructed from a designed redox-active tetrathiafulvalene (TTF) functionalized Schiff-base and the ditopic linker 4,4′-bipyridine (bpy). It exhibits an 8 K hysteretic SCO centred at T1/2 = 325 K which is coupled to changes in its dielectric constant. The crystal structures above and below the transition temperature reveal similar parallel linear ⋯Fe–bpy–Fe–bpy⋯ chains displaying expansion of the FeII octahedron in the HS state. Density functional theory (DFT) calculations reveal a concerted electronic charge and spin change represented by the Mülliken charge of the Fe and the magnitude and direction of the dipole moment which substantiate the experimental observations.

Graphical abstract: Enhanced dielectricity coupled to spin-crossover in a one-dimensional polymer iron(ii) incorporating tetrathiafulvalene

Supplementary files

Article information

Article type
Edge Article
Submitted
28 4 2020
Accepted
27 5 2020
First published
27 5 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2020,11, 6229-6235

Enhanced dielectricity coupled to spin-crossover in a one-dimensional polymer iron(II) incorporating tetrathiafulvalene

Y. Qiu, L. Cui, P. Cai, F. Yu, M. Kurmoo, C. F. Leong, D. M. D'Alessandro and J. Zuo, Chem. Sci., 2020, 11, 6229 DOI: 10.1039/D0SC02388D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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