Metal Complexes of Bridging Neutral Radical Ligands: pymDTDA and pymDSDA

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• 作者：Jian Wu ; Daniel J. MacDonald ; Rodolphe Cl茅rac ; Ie-Rang Jeon ; Michael Jennings ; Alan J. Lough ; James Britten ; Craig Robertson ; Paul A. Dube ; Kathryn E. Preuss
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：March 19, 2012
• 年：2012
• 卷：51
• 期：6
• 页码：3827-3839
• 全文大小：599K
• 年卷期：v.51,no.6(March 19, 2012)
• ISSN：1520-510X

文摘

Metal complexes of the 4-(2鈥?pyrimidyl)-1,2,3,5-dithiadiazolyl (pymDTDA) neutral radical ligand and its selenium analogue (pymDSDA) are presented. The following series of metal ions has been studied using M(hfac)₂ as the coordination fragment of choice (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato): Mn^II, Co^II, Ni^II, and Zn^II. The binuclear cobalt and nickel complexes of pymDTDA both exhibit ferromagnetic (FM) coupling between the unpaired electrons on the ligand and the metal ion, while the binuclear zinc complex of pymDTDA is presented as a comparative example incorporating a diamagnetic metal ion. The binuclear manganese complex of pymDTDA, reported in a preliminary communication, is compared to the pymDSDA analogue, and new insight into the magnetic behavior reveals that intermolecular magnetic coupling, mediated by chalcogen鈥搊xygen contacts, gives rise to a significant increase in the 蠂T product at low temperature. Surprisingly, the binuclear nickel complex of pymDSDA forms dimers in the solid state, as do the mononuclear complexes of cobalt and nickel with pymDTDA. In addition, mixed mononuclear/binuclear complexes of Mn- and Zn(pymDTDA) have been identified.