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Multi‐Magnetic Properties of a Novel SCO [Fe(3‐OMe‐Sal 2 trien)][Fe(tdas) 2 ]·CH 3 CN Salt
Author(s) -
Spitsytaliya,
Ovanesyan Nikolay,
Blagov Maxim,
Krapivin Vladimir,
Lobach Anatolii,
Dmitriev Alexei,
Simonov Sergey,
Zorina Leokadiya,
Pilia Luca,
Deplano Paola,
Vasiliev Alexander,
Maximova Olga,
Yagubskii Eduard
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.202000873
Subject(s) - chemistry , spin crossover , crystallography , density functional theory , magnetization , crystal structure , ion , salt (chemistry) , computational chemistry , organic chemistry , physics , quantum mechanics , magnetic field
The multi‐magnetic salt [Fe(3‐OMe‐Sal 2 trien)][Fe(tdas) 2 ] · CH 3 CN ( 1 ) has been prepared and fully characterized by a variety of methods. The crystal structure of 1 , determined at 150, 297 and 350 K, consists of alternating layers composed by a parallel arrangement of the chains of isolated π–π coupled cation pairs of [Fe(3‐OMe‐Sal 2 trien)] + and anion pairs of [Fe(tdas) 2 ] – . The complex magnetic behavior of this salt is consistent with the sum of the contributions from spin‐crossover (SCO) cations and strong antiferromagnetically (AFM) coupled dimeric [Fe(tdas) 2 ] 2 2– anions. The observed gradual thermally induced spin transition ( T 1/2 = 195 K) is relatable to the cation exhibiting disordering of ethylene (–CH 2 –CH 2 –) groups between two conformers with a narrow thermal hysteresis of 6 K. The dc magnetization measurements and 57 Fe Mössbauer spectroscopy at room temperature are in excellent agreement between γ HS (%) value and ratio of disordering of ethylene groups obtained from X‐ray analysis. Mössbauer spectra at 80 K and 296 K indicate a spin transition between S = 1/2 and S = 5/2 for the iron(III) saltrien‐cation and confirms S = 3/2 for the [Fe III (tdas) 2 ] – anion. The experimental results are supplemented with a theoretical Density Functional Theory (DFT) analysis.