Pressure‐Induced Enhancement of Magnetic‐Ordering Temperature in an Organic Radical to 70 K: A Magnetostructural Correlation |
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| Authors: | Richard I. Thomson Dr. Christopher M. Pask Dr. Gareth O. Lloyd Prof. Masaki Mito Prof. Jeremy M. Rawson |
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| Affiliation: | 1. Department of Chemistry, The University of Cambridge, Lensfield Road, Cambridge CB2 1EW (UK);2. Faculty of Engineering, Kyushu Institute of Technology, Kitakyushu, 804‐8550 (Japan);3. Department of Chemistry and Biochemistry, The University of Windsor, 401 Sunset Avenue, Windsor ON N9B 3P4 (Canada), Fax: (+1)?519‐973‐7098 |
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| Abstract: | ![]()
The structure of the canted antiferromagnet β‐p‐NCC6F4CNSSN ( 1 ) was determined from synchrotron powder‐diffraction studies in the pressure range 0–21.6 kbar. Radical 1 crystallizes in the orthorhombic space group Fdd2, but undergoes an asymmetric contraction of the unit‐cell size with increasing pressure. At the molecular level, this contraction of the unit cell is simultaneously accommodated by: 1) an increase in twist angle between aryl and heterocyclic rings; and 2) a shortening of the intermolecular S ??? N contacts, which propagate the magnetic‐exchange pathway. DFT calculations based on the structures in this pressure range revealed an increase in the magnetic‐exchange interaction (J) with increasing pressure, and an excellent correlation was observed between J and the magnetic‐ordering temperature, which increased from 36 K at ambient pressure up to 70 K at 16 kbar. |
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| Keywords: | dithiadiazolyl density functional calculations magnetic properties powder diffraction X‐ray diffraction |
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