A Ditopic O4S2 Macrocycle and Its Hard, Soft, and Hard/Soft Metal Complexes Exhibiting Endo-, Exo-, or Endo/Exocyclic Coordination: Synthesis, Crystal Structures, NMR Titration,
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- 作者：Hyunsoo Ryu ; Ki-Min Park ; Mari Ikeda ; Yoichi Habata ; Shim Sung Lee
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：April 21, 2014
- 年：2014
- 卷：53
- 期：8
- 页码：4029-4038
- 全文大小：554K
- 年卷期：v.53,no.8(April 21, 2014)
- ISSN：1520-510X
文摘
A 20-membered O4S2 macrocycle (L2) was synthesized as a ditopic ligating system toward hard and soft metal ions simultaneously. Five complexes (3鈥?b>7) of L2 with different structures and coordination modes, including discrete to infinite forms, mono- to heteronuclear, and endo- to exo- and endo/exocoordination, were prepared and structurally characterized. First, the reaction of L2 with Pb(ClO4)2路3H2O afforded a typical endocyclic mononuclear perchlorato complex [Pb(L2)(ClO4)2] (3) in which one lead(II) is surrounded by the macrocycle adopting a 鈥渢ight and bent鈥?conformation. Meanwhile, the reaction with a softer metal salt AgNO3 resulted in the formation of the dinuclear bis(macrocycle) complex [Ag2(L2)2(NO3)2] (4) in which two exocyclic silver(I) ions are doubly linked by two nitrate ions. The treatment of L2 with CuI gave a mixture of the exocyclic monomer complex [Cu(L2)I] (5) and the exocyclic dimer complex [(Cu2I2)(L2)2] (6), which were separated manually because of their brick and rhomboid shapes of the crystals, respectively. Furthermore, the reaction of L2 with a mixture of CuI and NaI afforded a photoluminescent heteronuclear complex [Na2(Cu6I8)(L2)2(CH3CN)4]n (7) in the endo/exocyclic coordination mode. In this case, the endocyclic sodium(I) complex units are linked by the double-open cubanes-type cluster Cu6I8, yielding a two-dimensional network. The structural and binding properties of the complex of L2 with silver(I) nitrate in solution were monitored by the NMR titration. Photophysical and thermal properties for complex 7 were also investigated and discussed.