Next Article in Journal
Functional Properties of the Catalytic Domain of Mouse Acidic Mammalian Chitinase Expressed in Escherichia coli
Next Article in Special Issue
Exploring the Nature of Silicon-Noble Gas Bonds in H3SiNgNSi and HSiNgNSi Compounds (Ng = Xe, Rn)
Previous Article in Journal
Effect of Porcine Akirin2 on Skeletal Myosin Heavy Chain Isoform Expression
Previous Article in Special Issue
Experimental and Theoretical Study of O-Substituent Effect on the Fluorescence of 8-Hydroxyquinoline
Article Menu
Issue 2 (February) cover image

Export Article

Open AccessArticle
Int. J. Mol. Sci. 2015, 16(2), 4007-4027;

Multiscale Experimental and Theoretical Investigations of Spin Crossover FeII Complexes: Examples of [Fe(phen)2(NCS)2] and [Fe(PM-BiA)2(NCS)2]

CNRS, Univ. Bordeaux, ICMCB, UPR 9048, F-33600 Pessac, France
These authors contributed equally to this work.
Author to whom correspondence should be addressed.
Academic Editor: Francesc Illas
Received: 24 December 2014 / Revised: 14 January 2015 / Accepted: 30 January 2015 / Published: 12 February 2015
(This article belongs to the Special Issue Chemical Bond and Bonding 2015)
Full-Text   |   PDF [2410 KB, uploaded 12 February 2015]   |  


For spin crossover (SCO) complexes, computation results are reported and confirmed with experiments at multiscale levels of the isolated molecule and extended solid on the one hand and theory on the other hand. The SCO phenomenon which characterizes organometallics based on divalent iron in an octahedral FeN6-like environment with high spin (HS) and low spin (LS) states involves the LS/HS switching at the cost of small energies provided by temperature, pressure or light, the latter connected with Light-Induced Excited Spin-State Trapping (LIESST) process. Characteristic infra red (IR) and Raman vibration frequencies are computed within density functional theory (DFT) framework. In [Fe(phen)2(NCS)2] a connection of selected frequencies is established with an ultra-fast light-induced LS → HS photoswitching mechanism. In the extended solid, density of state DOS and electron localization function (ELF) are established for both LS and HS forms, leading to characterizion of the compound as an insulator in both spin states with larger gaps for LS configuration, while keeping molecular features in the solid. In [Fe(PM-BiA)2(NCS)2], by combining DFT and classical molecular dynamics, the properties and the domains of existence of the different phases are obtained by expressing the potential energy surfaces in a short range potential for Fe–N interactions. Applying such Fe–N potentials inserted in a classical force field and carrying out molecular dynamics (MD) in so-called “semi-classical MD” calculations, lead to the relative energies of HS/LS configurations of the crystal and to the assessment of the experimental (P, T) phase diagram. View Full-Text
Keywords: spin-crossover complex; DFT; photo-switching; molecular dynamics; (P, T) phase diagram spin-crossover complex; DFT; photo-switching; molecular dynamics; (P, T) phase diagram

Figure 1

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

Share & Cite This Article

MDPI and ACS Style

Matar, S.F.; Guionneau, P.; Chastanet, G. Multiscale Experimental and Theoretical Investigations of Spin Crossover FeII Complexes: Examples of [Fe(phen)2(NCS)2] and [Fe(PM-BiA)2(NCS)2]. Int. J. Mol. Sci. 2015, 16, 4007-4027.

Show more citation formats Show less citations formats

Related Articles

Article Metrics

Article Access Statistics



[Return to top]
Int. J. Mol. Sci. EISSN 1422-0067 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top