Тип публикации: статья из журнала
Год издания: 2014
Идентификатор DOI: 10.1016/j.ica.2014.04.001
Ключевые слова: DFT calculation, Exchange interaction, Phenoxazin-1-one, Sn(IV) complexes, X-ray crystal structure
Аннотация: Two six-coordinate Sn(IV) complexes, bis-[2,4,6,8-tetra-(tert-butyl)-9- oxyphenoxazinyl-1-onolate]Sn(IV) 4 and bis-[2,4,6,8-tetra-(tert-butyl)- phenoxazinyl-1-onolate]Sn(IV) dichloride 5 with redox-active tridentate 2,4,6,8-tetra(tert-butyl)-9-hydroxyphenoxazin-1-one 2 and bidentate 1-H-1-oxo-2,4,6,8-tetra(tert-butyl) phenoxazine-1Показать полностью-one 3 ligands were synthesized and their molecular structures determined with the use of X-ray crystallography. Electronic structures of the complexes were investigated with DFT B3LYP*/6-311++G(d,p) calculations, SQUID magnetometry and EPR spectroscopy and assigned to the biradical Sn(IV)(CatNSQ)2 and Sn(IV)(ISQ)2Cl2 electromeric forms, where (CatNSQ) 2- and (ISQ)- are radical-anions formed by the ligands 2 and 3, correspondingly. Weak ferromagnetic coupling of the two paramagnetic centers was established in complex Sn(IV)(CatNSQ)2 with ligands 2, whereas in the same type complex formed by ligands 3 the coupling of the paramagnetic centers bears weak antiferromagnetic character. The calculated exchange coupling constants J for 4 and 5 (5 cm-1 and -8 cm -1, respectively) are in sufficiently good agreement with the values obtained from analysis of ?eff(T) dependences (3.5 cm-1 and -1 cm-1). © 2014 Elsevier B.V. All rights reserved.
Журнал: Inorganica Chimica Acta
Выпуск журнала: Vol. 418
Номера страниц: 66-72