Premium
Magnetic Properties of a New Hexahalorhenate(IV) Compound and Structural Comparison with Its Hexahaloplatinate(IV) Analog
Author(s) -
Piccinelli Fabio,
Bettinelli Marco,
Cano Joan,
Lloret Francesc,
Julve Miguel,
Dolmella Alessandro
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000199
Subject(s) - chemistry , rhenium , monoclinic crystal system , crystallography , magnetic susceptibility , ion , yield (engineering) , molecule , crystal structure , stereochemistry , inorganic chemistry , thermodynamics , organic chemistry , physics
Two mononuclear complexes of formula (Et 3 BzN) 2 [ReCl 6 ] ( 1 ) and (Et 3 BzN) 2 [PtCl 6 ] ( 2 ) (Et 3 BzN + = triethylbenzylammonium cation) have been synthesized in good yield (70 and 75 %, respectively) and structurally characterized. From a structural point of view, they both crystallized in the monoclinic centrosymmetric P 2 1 / n space group and the two molecular structures are almost perfectly superimposable, with only minor differences in the M–Cl bond lengths. Solid‐state direct‐current (dc) magnetic susceptibility analysis in the temperature range 1.9–300 K for 1 reveal the occurrence of magnetically isolated rhenium(IV) ions with a significant zero‐field splitting (zfs), D = +6.7 cm –1 (2 D being the energy gap between the M S = ±3/2 and M S = ±1/2 Kramers doublets). DFT, CASSCF and CASSCF/NEVPT2 theoretical calculations were carried out on the experimental geometry of the complex [ReCl 6 ] 2– in 1 to substantiate the parameters defining the zfs tensor. Alternating current (ac) magnetic susceptibility measurements of 1 in the temperature 2.0–10 K show incipient frequency–dependence of the out‐of‐phase signals below 3.0 K under non‐zero applied dc fields supporting a field–dependent Single Ion Single Molecule Magnet (SISMM) behaviour of this rhenium(IV) derivative.