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Magnetic Anisotropy of the Antiferromagnetic Ring [Cr 8 F 8 Piv 16 ]
Author(s) -
van Slageren Joris,
Sessoli Roberta,
Gatteschi Dante,
Smith Andrew A.,
Helliwell Madeleine,
Winpenny Richard E. P.,
Cornia Andrea,
Barra AnneLaure,
Jansen Aloysius G. M.,
Rentschler Eva,
Timco Grigore A.
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020104)8:1<277::aid-chem277>3.0.co;2-d
Subject(s) - antiferromagnetism , excited state , chemistry , anisotropy , tetragonal crystal system , magnetic anisotropy , condensed matter physics , electron paramagnetic resonance , ion , dipole , spin (aerodynamics) , molecular physics , crystallography , atomic physics , magnetic field , nuclear magnetic resonance , physics , magnetization , crystal structure , organic chemistry , quantum mechanics , thermodynamics
A new tetragonal ( P 42 1 2) crystalline form of [Cr 8 F 8 Piv 16 ] (HPiv=pivalic acid, trimethyl acetic acid) is reported. The ring‐shaped molecules, which are aligned in a parallel fashion in the unit cell, form almost perfectly planar, regular octagons. The interaction between the Cr III ions is antiferromagnetic ( J =12 cm −1 ) which results in a S =0 spin ground state. The low‐lying spin excited states were investigated by cantilever torque magnetometry (CTM) and high‐frequency EPR (HFEPR). The compound shows hard‐axis anisotropy. The axial zero‐field splitting (ZFS) parameters of the first two spin excited states ( S =1 and S =2, respectively) are D 1 =1.59(3) cm −1 or 1.63 cm −1 (from CTM and HFEPR, respectively) and D 2 =0.37 cm −1 (from HFEPR). The dipolar contributions to the ZFS of the S =1 and S =2 spin states were calculated with the point dipolar approximation. These contributions proved to be less than the combined single‐ion contributions. Angular overlap model calculations that used parameters obtained from the electronic absorption spectrum, showed that the unique axis of the single‐ion ZFS is at an angle of 19.3(1)° with respect to the ring axis. The excellent agreement between the experimental and the theoretical results show the validity of the used methods for the analysis of the magnetic anisotropy in antiferromagnetic Cr III rings.