Issue 30, 2015

Intermediate-paramagnetic phases with a half and a quarter spin entities in fluorinated biphenyl-3,5-diyl bis(tert-butyl nitroxides)

Abstract

A new ground-triplet biradical, 2′,5′-difluorobiphenyl-3,5-diyl bis(tert-butyl nitroxide), showed spin-transition-like behaviour at TC↑ = 182 K and TC↓ = 181 K. This compound had a quarter of the nominal amount of paramagnetic spins in the low-temperature phase and a half in the high-temperature phase. Another new 3′-monofluoro derivative maintained a half amount of the spins as a single solid phase, which is isomorphous to the high-temperature phase of the difluoro analogue. During the spin transition, a reversible bond formation–cleavage between nitrogen and oxygen atoms takes place at neighbouring nitroxide groups in an intermolecular fashion. These intermediate states emerge during multi-step spin transition from the unsymmetrical biradicals as designed.

Graphical abstract: Intermediate-paramagnetic phases with a half and a quarter spin entities in fluorinated biphenyl-3,5-diyl bis(tert-butyl nitroxides)

Supplementary files

Article information

Article type
Paper
Submitted
09 mars 2015
Accepted
04 avr. 2015
First published
08 avr. 2015

J. Mater. Chem. C, 2015,3, 7813-7818

Author version available

Intermediate-paramagnetic phases with a half and a quarter spin entities in fluorinated biphenyl-3,5-diyl bis(tert-butyl nitroxides)

T. Konno, H. Kudo and T. Ishida, J. Mater. Chem. C, 2015, 3, 7813 DOI: 10.1039/C5TC00668F

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