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Seeking Hidden Magnetic Phenomena by Theoretical Means in a Thiooxoverdazyl Adduct
Author(s) -
Vérot Martin,
Bréfuel Nicolas,
Pécaut Jacques,
Train Cyrille,
Robert Vincent
Publication year - 2012
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201100736
Subject(s) - antiferromagnetism , radical , benzoquinone , ferromagnetism , chemistry , adduct , crystallography , magnetic susceptibility , materials science , condensed matter physics , physics , organic chemistry , biochemistry
The oxidation of 1,5‐dimethyl‐3‐(2′‐pyridyl)‐6‐thiooxotetrazane (SvdH 3 py) by benzoquinone leads to a 1:1 adduct of 1,5‐dimethyl‐3‐(2′‐pyridyl)‐6‐thiooxoverdazyl radical (Svdpy) with hydroquinone (hq). The single‐crystal X‐ray diffraction of this adduct at room temperature (RT) shows that the radicals exhibit a slight curvature that leads to the formation of alternating head‐to‐tail (antiparallel) stacked 1D chains. Moreover, temperature‐dependent X‐ray measurements at 100, 200, and 303 K reveal that the lateral slippages between the radicals of the stacks | δ 1 | and | δ 2 | vary from 0.64 to 0.78 Å and 0.54 to 0.40 Å between 100 and 303 K. Despite the alternation of the inter‐radical distances and lateral slippages, the magnetic susceptibility data can be fitted with excellent agreement using a regular one‐dimensional antiferromagnetic chain model with J =−5.9 cm −1 . Wavefunction‐based calculations indicate an alternation of the magnetic interaction parameters correlated with the structural analysis at RT. Moreover, they demonstrate that the thermal slippage of the radicals induces a switching of the physical behavior, since the exchange interaction changes from antiferromagnetic (−0.9 cm −1 ) at 100 K to ferromagnetic (1.4 cm −1 ) at 303 K. The theoretical approach thus reveals a much richer magnetic behavior than the analysis of the magnetic susceptibility data and ultimately questions the relevance of a spin‐coupled picture based on temperature‐independent parameters.