Abstract
Single crystal structural analysis of [FeII(tame)2]Cl2MeOH (tame=1,1,1-tris(aminomethyl)ethane) as a function of temperature reveals a smooth crossover between a high temperature high-spin octahedral d6 state and a low temperature low-spin ground state without change of the symmetry of the crystal structure. The temperature at which the high and low spin states are present in equal proportions is T1/2=140K. Single crystal, variable-temperature optical spectroscopy of [FeII(tame)2]Cl2MeOH is consistent with this change in electronic ground state. These experimental results confirm the spin activity predicted for [FeII(tame)2]2+ during its de novo artificial evolution design as a spin-crossover complex [Chem. Inf. Model. 2015, 55, 1844], offering the first experimental validation of a functional transition-metal complex predicted by such in silico molecular design methods. Additional quantum chemical calculations offer, together with the crystal structure analysis, insight into the role of spin-passive structural components. A thermodynamic analysis based on an Ising-like mean field model (Slichter-Drickammer approximation) provides estimates of the enthalpy, entropy and cooperativity of the crossover between the high and low spin states.
Original language | English |
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Pages (from-to) | 5082-5085 |
Number of pages | 4 |
Journal | Chemistry - A European Journal |
Volume | 24 |
Issue number | 20 |
Early online date | 29 Jan 2018 |
DOIs | |
Publication status | Published - 6 Apr 2018 |
Bibliographical note
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.Keywords
- amines
- density functional calculations
- iron
- optical spectroscopy
- spin crossover
ASJC Scopus subject areas
- Catalysis
- Organic Chemistry
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