Transition Metal Complexes and Radical Anion Salts of 1,10-Phenanthroline Derivatives Annulated with a 1,2,5-Tiadiazole and 1,2,5-Tiadiazole 1,1-Dioxide Moiety: Multidimensional Crystal Structures and Various Magnetic Properties
Advances in the molecular variety and the elucidation of the physical properties of 1,10-phenanthroline annulated with 1,2,5-thiadiazole and 1,2,5-thiadiazole 1,1-dioxide moieties have been achieved, and are described herein. A 1,2,5-thiadiazole compound, [1,2,5]thiadiazolo[3,4- f][1,10]phenanthroline (tdap), was used as a ligand to create multidimensional network structures based on S？？？S and S？？？N intermolecular interactions. A 1,2,5-thiadiazole 1,1-dioxide compound, [1,2,5] thiadiazolo[3,4- f][1,10]phenanthroline, 1,1-dioxide (tdapO 2), was designed to create a stable radical anion, as well as good network structures. Single crystal X-ray structure analyses revealed that transition metal complexes of tdap, and radical anion salts of tdapO 2 formed multidimensional network structures, as expected. Two kinds of tdap iron complexes, namely [Fe(tdap) 2(NCS) 2] and [Fe(tdap) 2(NCS) 2]？MeCN exhibited spin crossover transitions, and their transition temperatures showed a difference of 150 K, despite their similar molecular structures. Magnetic measurements for the tdapO 2 radical anion salts revealed that the magnetic coupling constants between neighboring radical species vary from strongly antiferromagnetic ( J = ？320 K) to ferromagnetic ( J = 24 K), reflecting the differences in their π overlap motifs.
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Crystallographic data for the compounds discussed in this review that have not previously been published are available through Cambridge Crystallographic Data Centre (CCDC): CCDC 969113 ([Co(tdap)2(NCS)2]), CCDC 969114 ([Mn(tdap)2Cl2]), CCDC 969115 ([Mn(tdap)2(NCS)2]？MeCN), CCDC 969116 ([Fe(tdap)2(NCS)2]？MeCN at 120 K), CCDC 969117 ([Fe(tdap)2(NCS)2]？MeCN at 320 K), CCDC 969118 ([Co(tdap)2(NCS)2]？MeCN), CCDC 969119 ([Ni(tdap)2(NCS)2]？MeCN), CCDC 969120 ([Cu(tdap)2(NCS)2]？MeCN), CCDC 969121 ([Zn(tdap)2(NCS)2]？MeCN), CCDC 969122 ([Cu2(tdap)2(NCS)2]), CCDC 969123 ([Cu2(tdap)2(NCS)4]), and CCDC 9691224 ([CoCp]2？tdapO2). These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336033; E-mail: deposit@ccdc.cam.ac.uk).
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