Metal complexes of bridging neutral radical ligands: pymDTDA and pymDSDA

Inorganic Chemistry
Jian WuKathryn E Preuss

Abstract

Metal complexes of the 4-(2'-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-oxygen contacts, gives rise to a significant increase in the χT 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.

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Citations

Mar 23, 2017·Chemical Communications : Chem Comm·R Alex MayoKathryn E Preuss
Dec 1, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Hinako KawakamiTakayuki Ishida
Jul 28, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Jian WangXin-Yi Wang
Aug 25, 2020·Acta Crystallographica Section B, Structural Science, Crystal Engineering and Materials·Matthew G ReevesSimon Parsons
Oct 5, 2012·Chemical Communications : Chem Comm·David J SullivanKathryn E Preuss
Sep 6, 2013·Chemical Communications : Chem Comm·Elisabeth M FatilaKathryn E Preuss
Jun 16, 2015·Chemistry : a European Journal·Toby J WoodsKim R Dunbar
Aug 30, 2013·Journal of the American Chemical Society·Elisabeth M FatilaKathryn E Preuss
Mar 15, 2015·Journal of the American Chemical Society·Stephen M WinterRichard T Oakley
Sep 20, 2017·Journal of the American Chemical Society·Delia A HaynesOrde Q Munro

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