Strong supramolecular-based magnetic exchange in pi-stacked radicals. Structure and magnetism of a hydrogen-bonded verdazyl radical : hydroquinone molecular solid
Artikel i vetenskaplig tidskrift, 2001

The X-ray crystal structure and magnetic properties of a molecular crystal consisting of 1,5-dimethyl-3-(2-pyridyl)-6-oxoverdazyl radical and hydroquinone (pyvd:hq) are presented. The structure contains a two-dimensional network of hydrogen bonds involving the hydroquinones and the pyridine ring of the pyvd radical. The radicals adopt an unusual head-over-tail (antiparallel) jr-stacked array perpendicular to the hydrogen-bonded planes. The variable-temperature magnetic susceptibility data can be modeled using a one-dimensional antiferromagnetic chain model, with J = -58 cm(-1). The strength of the magnetic coupling is very unusual because there are no close intermolecular radical-radical contacts to provide conventional pathways for magnetic interactions. A pathway for coupling is proposed involving the mediation of magnetic exchange interactions between radical centers by the pyridine rings. Density functional calculations on the pyvd radical, as well as aggregates thereof based on the X-ray structure, have been employed in attempts to understand the possible mechanisms by which the strong magnetic interactions are achieved.

organic ferromagnet

nitronyl nitroxide radicals

density-functional calculations

5-triphenyl-6-oxoverdazyl

transition

ferromagnetic interactions

design

3

energy

approximation

1

crystals

Författare

R. G. Hicks

M. T. Lemaire

Lars Öhrström

Institutionen för oorganisk kemi

J. F. Richardson

L. K. Thompson

Z. Q. Xu

Journal of the American Chemical Society

Vol. 123 7154-7159

Ämneskategorier

Kemi