Kulmaczewski, R and Halcrow, MA orcid.org/0000-0001-7491-9034 (2016) Structures and Spin States of Crystalline [Fe(NCS)2L2] and [FeL3]2+ Complexes (L = an Annelated 1,10-Phenanthroline Derivative). CrystEngComm, 18 (14). pp. 2570-2578.
Abstract
The phase behaviour and spin states of [Fe(NCS)2(dpq)2] (1; dpq = dipyrido[3,2-f:2′,3′-h]quinoxaline), [Fe(NCS)2(dppz)2] (2; dppz = dipyrido[3,2-a:2′3′-c]phenazine) and [Fe(NCS)2(dppn)2] (3; dppn = dipyrido[3,2-a:2′3′-c]benzophenazine) have been investigated. Solvent-free 1 and 2 are isostructural and low-spin in the crystalline state, in contrast to previously published 2·py (py = pyridine) which exhibits a hysteretic spin-crossover (SCO) transition near 140 K. The inactivity of 1 and 2 towards SCO may relate to their more crowded intermolecular lattice environment, particularly two very short intermolecular anion⋯π contacts involving the NCS− ligands. Two solvate phases of 1 are also described, including 1·2py which undergoes gradual SCO with T½ca. 188 K. Bulk samples of 2 and 3 are predominantly low-spin and isostructural with the crystals of 2 by powder diffraction, but bulk samples of 1 contain an extra phase that exhibits hysteretic SCO, but was not crystallographically characterised. Crystal structures of low-spin [Fe(dppz)3][ClO4]2 (4) and a solvate of [Fe(dppn)3][BF4]2 (5) are also described, which are the first homoleptic complexes of these ligands to be crystallographically characterised.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © The Royal Society of Chemistry 2016. This is an author produced version of a paper published in CrystEngComm. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) |
Funding Information: | Funder Grant number EPSRC EP/K012568/1 |
Depositing User: | Symplectic Publications |
Date Deposited: | 07 Oct 2016 14:02 |
Last Modified: | 12 Apr 2017 04:14 |
Published Version: | http://dx.doi.org/10.1039/C6CE00163G |
Status: | Published |
Publisher: | Royal Society of Chemistry |
Identification Number: | 10.1039/C6CE00163G |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:96448 |