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Magnetic properties and crystal structures of 1,5-diphenylverdazyls with electron acceptor groups in the 3-position

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Gleiter,  Marco R.
Department of Organic Chemistry, Max Planck Institute for Medical Research, Max Planck Society;

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Krieger,  Claus
Department of Organic Chemistry, Max Planck Institute for Medical Research, Max Planck Society;

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Neugebauer,  Franz A.
Department of Organic Chemistry, Max Planck Institute for Medical Research, Max Planck Society;

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Citation

Mito, M., Takeda, K., Mukai, K., Azuma, N., Gleiter, M. R., Krieger, C., et al. (1997). Magnetic properties and crystal structures of 1,5-diphenylverdazyls with electron acceptor groups in the 3-position. The Journal of Physical Chemistry B, 101(46), 9517-9524. doi:10.1021/jp972195b.


Cite as: https://hdl.handle.net/11858/00-001M-0000-002B-2243-4
Abstract
The magnetic properties of four diphenylverdazyls (2−5) with electron acceptor groups in the 3-position were studied by measuring the magnetic susceptibility and heat capacity. The crystal structures of 3 and 4 were determined, and for 2 the crystal structure analysis led to an improved refinement. Verdazyl 2 was found to be an antiferromagnet with a Neel temperature of TN = 1.16 ± 0.04 K. Above the transition temperature TN, 2 behaves as a quasi-one-dimensional Heisenberg ferromagnet with the intrachain exchange interaction of 2J/kB = +7.0 ± 1.0 K. The interchain exchange interaction zJ‘/kB was estimated to be −1.5 ± 0.2 K, where z is the number of interchain bonds per spin. On the other hand, 3 and 5 behave as 1D nonalternating and alternating Heisenberg antiferromagnets with an exchange interaction of 2J/kB = −11.6 K and 2J1/kB = −113 K (alternation parameter α = J2/J1 = 0.4), respectively. The susceptibility of 4 follows the Curie−Weiss law with a negative Weiss constant of −18 K above 100 K. Below 100 K, 4 showed anomalous magnetic behavior that cannot be explained by a simple model. The magnetic properties of 2−4 are discussed based on the results obtained by crystal structure analyses.