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Crystals 2016, 6(3), 30; doi:10.3390/cryst6030030

Thermally Activated Paramagnets from Diamagnetic Polymers of Biphenyl-3,5-diyl Bis(tert-butyl Nitroxides) Carrying Methyl and Fluoro Groups at the 2’- and 5’-Positions

Department of Engineering Science, The University of Electro-Communications, Chofu, Tokyo 182-8585, Japan
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Author to whom correspondence should be addressed.
Academic Editor: Martin T. Lemaire
Received: 15 February 2016 / Revised: 12 March 2016 / Accepted: 15 March 2016 / Published: 22 March 2016
(This article belongs to the Special Issue High Spin Molecules)
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Abstract

Three new biradicals—2’,5’-dimethyl-, 2’-fluoro-5’-methyl-, and 5’-fluoro-2’-methyl- biphenyl-3,5-diyl bis(tert-butyl nitroxides)—were synthesized. The magnetic susceptibility measurements revealed their diamagnetism below and around room temperature. The nitroxide groups are located close to each other in an intermolecular fashion to form a weakly covalent head-to-tail (NO)2 ring. Biradical molecules are connected on both radical sites, constructing a diamagnetic chain. The dimethyl derivative underwent a structural phase transition at 83 °C, clarified via differential scanning calorimetry and powder X-ray diffraction, and a paramagnetic solid phase with S = 1 irreversibly appeared. The other analogues exhibited a similar irreversible upsurge of the magnetic susceptibility on heating, but the transition was characterized as the melting. View Full-Text
Keywords: triplet; nitroxide; aminoxyl; spin-polarization; intermolecular coupling; structural phase transition; dimerization triplet; nitroxide; aminoxyl; spin-polarization; intermolecular coupling; structural phase transition; dimerization
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Yoshitake, T.; Kudo, H.; Ishida, T. Thermally Activated Paramagnets from Diamagnetic Polymers of Biphenyl-3,5-diyl Bis(tert-butyl Nitroxides) Carrying Methyl and Fluoro Groups at the 2’- and 5’-Positions. Crystals 2016, 6, 30.

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