Synthesis and study of Cu-II complex with nitroxide, a jumping crystal analog

Synthesis and study of Cu-II complex with nitroxide, a jumping crystal analog Full article

Journal

Russian Chemical Bulletin
ISSN: 1066-5285 , E-ISSN: 1573-9171

Output data

Year: 2017, Volume: 66, Number: 2, Pages: 222-230 Pages count : 9 DOI: 10.1007/s11172-017-1722-y

Tags

Cu2+; nitroxide radicals; X-ray diffraction; magnetic properties

Authors

Sagdeev R.Z. ^1,2 , Tolstikov S.E. ¹ , Fokin S.V. ¹ , Obsharova I.V. ¹ , Tumanov S.V. ^1,3 , Veber S.L. ^1,3 , Romanenko G.V. ¹ , Bogomyakov A.S. ¹ , Fedin M.V. ^1,3 , Tretyakov E.V. ⁴ , Halcrow M. ⁵ , Ovcharenko V.I. ¹

Affiliations

1	(Данные Web of science) Russian Acad Sci, Int Tomog Ctr, Siberian Branch, 3a Ul Inst Skaya, Novosibirsk 630090, Russia
2	(Данные Web of science) Kazan Volga Reg Fed Univ, 18 Ul Kremlevskaya, Kazan 420008, Russia
3	(Данные Web of science) Novosibirsk State Univ, 2 Ul Pirogova, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, 9 Prosp Akad Lavrenteva, Novosibirsk 630090, Russia
5	(Данные Web of science) Univ Leeds, Leeds LS2 9JT, W Yorkshire, England

We synthesized 1-ethylimidazolyl-substituted nitronyl nitroxides, i.e., 2-(1-ethylimidazol-4-yl)- (L-4Et) and 2-(1-ethylimidazol-5-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 3-oxide-1-oxyl (L-5Et). The stable radical L-5Et is an ethyl analog of 2-(1-methylimidazol-5-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 3-oxide-1-oxyl (L-5Me) described earlier, the reaction of which with Cu(hfac)(2) (hfac is 1,1,1,5,5,5-hexafluoropentane-2,4-dionate) leads to the formation of the [Cu(hfac)(2)(L-5Me)(2)] jumping crystals. The reaction of Cu(hfac)(2) with L-5Et with reagent ratios 1: 2 and 1: 1 yields heterospin complexes [Cu(hfac)(2)(L-5Et)(2)] and [Cu(hfac)(2)L-5Et](2), respectively. X-ray diffraction study of the mononuclear complex [Cu(hfac)(2)(L-5Et)(2)] determined that the compound has a packing similar to that of jumping crystals studied earlier, with the only difference being that the O...O contacts between neigh- boring nitroxide groups were found to be 0.3-0.5 longer than in [Cu(hfac)(2)(L-5Me)(2)]. As a result of the lengthening of these contacts, [Cu(hfac)(2)(L-5Et)(2)] crystals lack chemomechanical activi- ty. We found that when cooling crystals of binuclear complex [Cu(hfac)(2)L-5Et](2) below 50 K, the antiferromagnetic exchange between unpaired electrons of the > N-aEuro cent O groups of neighboring molecules leads to the full spin-pairing of the nitroxides, with only the Cu2+ ions contributing to the residual paramagnetism of the compound.

Sagdeev R.Z. , Tolstikov S.E. , Fokin S.V. , Obsharova I.V. , Tumanov S.V. , Veber S.L. , Romanenko G.V. , Bogomyakov A.S. , Fedin M.V. , Tretyakov E.V. , Halcrow M. , Ovcharenko V.I.
Synthesis and study of Cu-II complex with nitroxide, a jumping crystal analog
Russian Chemical Bulletin. 2017. V.66. N2. P.222-230. DOI: 10.1007/s11172-017-1722-y WOS Scopus РИНЦ

Сагдеев Р.З. , Толстиков С.Е. , Фокин С.В. , Обшарова И.В. , Туманов С.В. , Вебер С.Л. , Романенко Г.В. , Богомяков А.С. , Федин М.В. , Третьяков Е.В. , Халкроу М. , Овчаренко В.И.
Синтез и исследование комплекса cuii с нитроксилом - аналога "прыгающих" кристаллов
Известия Академии наук. Серия химическая.(RUSS CHEM B+). 2017. №2. С.222-230. РИНЦ

Published print:	Feb 1, 2017
Published online:	Jul 7, 2017

Web of science	WOS:000405088100004
Scopus	2-s2.0-85021830367
Elibrary	31057093
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