Please use this identifier to cite or link to this item:
For citation please use:
Main Title: Bulk spin-crossover in the complex [FeL(NCS)(2)] of a tris(pyridyl)ethane-derived N-4-ligand-a temperature-dependent crystallographic study
Author(s): Wiedemann, Dennis
Grohmann, Andreas
Type: Article
Abstract: We have recently shown that the vacuum-deposited complex [FeIIL(NCS)2] (L: 1-{6-[1,1-di(pyridin-2-yl)ethyl]-pyridin-2-yl}-N,N-dimethylmethanamine) is capable of a thermally induced spin crossover (SCO) in direct contact with a graphite surface. The SCO significantly differs from the transition behaviour in the bulk phase (powder). In the present work, the assumption of virtually no intermolecular interaction in the powder is confirmed by comparison with the spin transition in acetone solution (T1/2 = 234[3] K, ΔT80 = 58[4] K), as monitored by temperature-dependent UV/Vis spectroscopy. The complex crystallises from chlorocarbons in the form of a number of pseudopolymorphs. Amongst these, the sufficiently stable solvate [FeIIL(NCS)2]·CHCl3 is investigated by variable-temperature single-crystal X-ray diffractometry. Its SCO behaviour (T1/2 = 240[3] K, ΔT80 = 35[4] K) correlates with features of molecular structure that are unambiguously identified by analysis of the tensor of thermal expansion. Following comprehensive comparison of spin-transition properties in different states of aggregation (also in relation to the newly synthesised high-spin iron(II) and iron(III) complexes [FeIICl2L] and [FeIIICl2L]PF6), a mode of adsorption on graphite surfaces is proposed, that complies with all previous findings.
Issue Date: 2014
Date Available: 23-Jun-2016
Language Code: en
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Sponsor/Funder: DFG, SFB 658, Elementarprozesse in molekularen Schaltern auf Oberflächen
Journal Title: Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry
Publisher: Royal Society of Chemistry
Volume: 43
Issue: 6
Publisher DOI: 10.1039/c3dt53070a
Page Start: 2406
Page End: 2417
EISSN: 1477-9226
Notes: Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.
TU Affiliation(s): Fak. 2 Mathematik und Naturwissenschaften » Inst. Chemie
Appears in Collections:Technische Universität Berlin » Publications

Files in This Item:
Format: Adobe PDF | Size: 721.57 kB
DownloadShow Preview

Item Export Bar

Items in DepositOnce are protected by copyright, with all rights reserved, unless otherwise indicated.