Heterospin complex showing spin transition at room temperature

• Published in: Polyhedron Vol. 100; pp. 132 - 138
• Main Authors: Tolstikov, S.E., Artiukhova, N.A., Romanenko, G.V., Bogomyakov, A.S., Zueva, E.M., Barskaya, I.Yu, Fedin, M.V., Maryunina, K.Yu, Tretyakov, E.V., Sagdeev, R.Z., Ovcharenko, V.I.
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 04.11.2015; Elsevier
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Crystallography; Cu(II) complexes; Magnetostructural correlations; Nitroxides; Phase transitions; Physical Sciences; Science & Technology; Spin crossover; Cu(II) complexes; Magnetostructural correlations; Nitroxides; Phase transitions; Spin crossover; DESIGN; COPPER(II); AB-INITIO ANALYSIS; NITRONYL NITROXIDES; 3-IMIDAZOLINE NITROXIDES; RADICALS; MAGNETIC-PROPERTIES; CU(II) BISCHELATE COMPLEXES
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2015.07.029

Novel binuclear [Cu(hfac)2LMe]2, [Cu(hfac)2LMe-CP]2 and chain polymer {[[Cu(hfac)2]2LMe2][Cu(hfac)2]}∞ heterospin complexes revealed spin-crossover-like phenomenon. [Display omitted] New nitronyl nitroxides LMe and LMe-CP containing a 4-methylpyridin-3-yl substituent were synthesized. It was found that the interaction of Сu(hfac)2 with LMe and LMe-CP gave binuclear [Cu(hfac)2LMe]2 and [Cu(hfac)2LMe-CP]2·Solv (Solv=n-C6H14, n-C10H22, n-C16H34) and chain polymer {[[Cu(hfac)2]2LMe2][Cu(hfac)2]}∞ heterospin complexes. An important structural peculiarity of LMe and LMe-CP is a large dihedral angle between the planes of the O–N−CN→O paramagnetic fragment and the pyridine ring: 55.2 and 56.1°, respectively. The presence of a methyl group in the pyridine ring of the nitroxide molecule in {[[Cu(hfac)2]2LMe2][Cu(hfac)2]}∞ proved favorable for spin transition at nearly room temperature.