Issue 21, 2019

Heteroatom substitution effects in spin crossover dinuclear complexes

Abstract

We probe the effect of heteroatom substitution on the spin crossover (SCO) properties of dinuclear materials of the type [Fe2(NCX)4(R-trz)5]·S (X = S, Se; S = solvent; R-trz = (E)-N-(furan-2-ylmethylene)-4H-1,2,4-triazol-4-amine (furtrz); (E)-N-(thiophen-2-ylmethylene)-4H-1,2,4-triazole-4-amine (thtrz)). For the furtrz family ([Fe2(NCX)4(furtrz)5]·furtrz·MeOH; X = S (furtrz-S) and X = Se (furtrz-Se)) gradual and incomplete one-step SCO transitions are observed (furtrz-S (T1/2 = 172 K) and furtrz-Se (T1/2 = 205 K)) and a structural evolution from [HS–HS] to [HS–LS] per dinuclear species. Contrasting this, within the thtrz family ([Fe2(NCX)4(thtrz)5]·4MeOH; X = S (thtrz-S) and X = Se (thtrz-Se)) more varied SCO transitions are observed, with thtrz-S being SCO-inactive (high spin) and thtrz-Se showing a rare complete two-step SCO transition (T1/2(1,2) = 170, 200 K) in which the FeII sites transition from [HS–HS] to [HS–LS] to [LS–LS] per dinuclear unit with no long range ordering of spin-states at the intermediate plateau. Detailed structure–function analyses have been conducted within this growing dinuclear family to rationalise these diverse spin-switching properties.

Graphical abstract: Heteroatom substitution effects in spin crossover dinuclear complexes

Supplementary files

Article information

Article type
Paper
Submitted
20 Dec 2018
Accepted
11 Mar 2019
First published
18 Mar 2019

Dalton Trans., 2019,48, 7337-7343

Heteroatom substitution effects in spin crossover dinuclear complexes

S. Zaiter, C. Kirk, M. Taylor, Y. M. Klein, C. E. Housecroft, N. F. Sciortino, J. E. Clements, R. I. Cooper, C. J. Kepert and S. M. Neville, Dalton Trans., 2019, 48, 7337 DOI: 10.1039/C8DT05010D

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