Structural Diversity and Thermochromic Properties of Iodobismuthate Materials Containing d-Metal Coordination Cations: Observation of a High Symmetry [Bi3I11]2鈭?/sup> Anion

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• 作者：Andrea M. Goforth ; Meredith A. Tershansy ; Mark D. Smith ; LeRoy Peterson ; Jr. ; Jennifer G. Kelley ; William J. I. DeBenedetti ; Hans-Conrad zur Loye
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：January 26, 2011
• 年：2011
• 卷：133
• 期：3
• 页码：603-612
• 全文大小：532K
• 年卷期：v.133,no.3(January 26, 2011)
• ISSN：1520-5126

文摘

Six new inorganic鈭抩rganic salts, all containing iodobismuthate anions and d-metal coordination cations, were synthesized solvothermally from reactions of bismuth iodide, a transition metal (M) nitrate salt (M = Co, Fe or Zn), and a heterocyclic, chelating organic ligand: 1,10-phenanthroline (1,10-phen), 3,4,7,8-tetramethyl-1,10-phenanthroline (TMphen), or 2,2鈥?6鈥?2鈥测€?terpyridine (tpy). All six compounds were structurally analyzed by single crystal X-ray diffraction, including variable temperature crystallographic analysis to monitor for structural changes. Furthermore, those containing novel anions and achieved in high yield were additionally characterized by solid-state UV visible spectroscopy at room temperature. [Co(1,10-phen)₃][Bi₃I₁₁] (1), [Fe(1,10-phen)₃][Bi₃I₁₁] (2), and [Zn(1,10-phen)₃][Bi₃I₁₁] (3) are isostructural. They crystallize in the monoclinic space group P2₁/n and contain the unprecedented iodobismuthate anion, [Bi₃I₁₁]^{2鈭?/sup>, which exhibits near D_3h symmetry and has an unusual arrangement of three cis face-sharing BiI₆ octahedra. [Co(TMPhen)₃]₂[Bi₂I₉][I] (4), which crystallizes in the trigonal space group P-31c, and [Co(tpy)₂]₂[Bi₂I₉][I] (5) and [Zn(tpy)₂]₂[Bi₂I₉][I] (6), which are isostructural and crystallize in the monoclinic space group C2/c, contain the discrete binuclear [Bi₂I₉]3鈭?/sup> anion, common in previously reported iodobismuthate compounds. In addition they contain unusual isolated I鈭?/sup> anions, which are rarely encountered in iodobismuthate phases. Compounds 1鈭?b>6 show constitutional similarities while utilizing different organic ligands and illustrate the sensitive dependence of reaction conditions on the identity of the halometalate anion formed. Additionally, all six compounds and the starting material BiI₃ are thermochromic; the origin of this behavior is spectroscopically and crystallographically investigated.}