Kershaw Cook, L, Mohammed, R, Sherborne, G et al. (3 more authors) (2015) Spin state behavior of iron(II)/dipyrazolylpyridine complexes. New insights from crystallographic and solution measurements. Coordination Chemistry Reviews, 289-29 (1). 2 - 12. ISSN 0010-8545
Abstract
The isomeric complexes [Fe(1-bpp)2]2+ and [Fe(3-bpp)2]2+ (1-bpp=2,6-di[pyrazol-1-yl]pyridine; 3-bpp=2,6-di[1H-pyrazol-3-yl]pyridine) and their derivatives are some of the most widely investigated complexes in spin-crossover research. This article addresses two unique aspects of their spin-state chemistry. First, is an unusual structural distortion in the high-spin form that can inhibit spin-crossover in the solid state. A new analysis of these structures using continuous shape measures has explained this distortion in terms of its effect on the metal coordination geometry, and has shown that the most highly distorted structures are a consequence of crystal packing effects. Second, solution studies have quantified the influence of second-sphere hydrogen bonding on spin-crossover in [Fe(3-bpp)2]2+, which responds to the presence of different anions and solvents (especially water). Previously unpublished data from the unsymmetric isomer [Fe(1,3-bpp)2]2+ (1,3-bpp=2-[pyrazol-1-yl]-6-[1H-pyrazol-3-yl]pyridine) are presented for comparison. Modifications to the structure of [Fe(3-bpp)2]2+, intended to augment these supramolecular effects, are also described.
Metadata
Item Type: | Article |
---|---|
Authors/Creators: |
|
Copyright, Publisher and Additional Information: | © 2014 Elsevier B.V. All rights reserved. This is an author produced version of a paper published in Coordination Chemistry Reviews. Uploaded in accordance with the publisher's self-archiving policy. |
Keywords: | Evans method; Iron complexes; Shape measures; Spin-crossover; Tridentate ligands |
Dates: |
|
Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 11 Aug 2015 14:23 |
Last Modified: | 20 Oct 2015 14:10 |
Published Version: | http://dx.doi.org/10.1016/j.ccr.2014.08.006 |
Status: | Published |
Publisher: | Elsevier |
Identification Number: | 10.1016/j.ccr.2014.08.006 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:88522 |