1. Magnetization Slow Dynamics in Ferrocenium Complexes
- Author
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Mei Ding, Mathieu Rouzières, Jeremy M. Smith, Martín Amoza, Joshua Telser, Wesley A. Hoffert, Tarik J. Ozumerzifon, David L. Tierney, Matthew P. Shores, Eliseo Ruiz, Anne K. Hickey, Maren Pink, Rodolphe Clérac, Department of Chemistry, Indiana University, Indiana University [Bloomington], Indiana University System-Indiana University System, Roosevelt University, Department of Biological, Chemical, and Physical Sciences, Department of Chemistry and Biochemistry, Departament de Quimica Inorganica, Institut de Recerca de Quimica Teorica i Computational, Centre de recherches Paul Pascal (CRPP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry, Colorado State University, Colorado State University [Fort Collins] (CSU), Departament de Quimica Inorganica, and Universitat de Barcelona (UB)
- Subjects
Electronic structure ,Metalls de terres rares ,Estructura electrònica ,010402 general chemistry ,01 natural sciences ,Catalysis ,symbols.namesake ,Magnetization ,Ab initio quantum chemistry methods ,Magnetic properties ,single-molecule magnets ,Quantum ,Propietats magnètiques ,010405 organic chemistry ,Chemistry ,ab initio calculations ,Organic Chemistry ,Relaxation (NMR) ,Rare earth metals ,[CHIM.MATE]Chemical Sciences/Material chemistry ,General Chemistry ,metallocenes ,electronic structure ,0104 chemical sciences ,Crystallography ,Magnet ,Excited state ,symbols ,magnetic properties ,Raman spectroscopy - Abstract
International audience; The single-molecule magnet (SMM) properties of a series of ferrocenium complexes, [Fe(h5-C5R5)2]+ (R=Me, Bn), are reported. In the presence of an applied dc field, the slow dynamics of the magnetization in [Fe(h5-C5Me5)2]BArF are revealed. Multireference quantum mechanical calculationsshow a large energy difference between the ground and first excited states, excluding the commonly invoked, thermally activated (Orbach-like) mechanism of relaxation. In contrast, a detailed analysis of the relaxation time highlights that both direct and Raman processes are responsible forthe SMM properties. Similarly, the bulky ferrocenium complexes, [Fe(h5-C5Bn5)2]BF4 and [Fe(h5-C5Bn5)2]PF6, also exhibit magnetization slow dynamics, however an additional relaxation process is clearly detected for these analogous systems.
- Published
- 2019
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