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<p>Reaction of BiI<sub>3</sub>/CuI or SbI<sub>3</sub>/CuI mixtures with the cyclic thioalkanes 1,3-dithiolane (DTL) or 1,4,7-trithiacyclononane (9S3) in toluene yielded the compounds BiCu<sub>3</sub>I<sub>6</sub>(DTL)<sub>3</sub> (<b>1</b>), SbCu<sub>3</sub>I<sub>6</sub>(DTL)<sub>3</sub> (<b>2</b>), and Bi<sub>2</sub>Cu<sub>3</sub>I<sub>9</sub>(9S3)<sub>4</sub> (<b>3</b>). All compounds were characterized via single crystal X-ray structure determination, powder X-ray diffraction, thermogravimetric analysis, elemental analysis, infrared, and diffuse reflectance spectroscopy. In all cases, sulfur centers bond only to Cu(I). Compounds <b>1</b> and <b>2</b> consist of isostructural 1D linear chain networks consisting of EI<sub>6</sub> octahedra (E = Bi, Sb) in which three mutually <i>cis</i> edges are capped with Cu(I) centers via μ<sub>2</sub>-I forming an ECu<sub>3</sub>I<sub>6</sub> cluster. All three DTL ligands are bidentate. Two DTL ligands bridge pairs of adjacent copper atoms in the ECu<sub>3</sub>I<sub>6</sub> cluster. Bridging by the remaining DTL links the clusters into infinite chains, …[ECu<sub>3</sub>I<sub>6</sub>(DTL)<sub>2</sub>](DTL)… Compound <b>3</b> displays a unique ionic structure, [Cu<sub>5</sub>(9S3)<sub>7</sub>]<sup>5+</sup>[Bi<sub>4</sub>CuI<sub>18</sub>(9S3)]<sup>5−</sup>. The cation is composed of a central 9S3 ligand that bridges disordered duos/trios of [Cu(9S3)]<sup>+</sup> units, yielding [Cu<sub>2.5</sub>(9S3)<sub>3.5</sub>]<sup>2.5+</sup>. The anion consists of half-independent face-sharing double octahedron, [Bi<sub>2</sub>I<sub>9</sub>]<sup>3−</sup> in which one of the trio of μ<sub>2</sub>-I centers further coordinates a half [Cu(9S3)]<sup>+</sup> unit, yielding [Bi<sub>2</sub>Cu<sub>0.5</sub>I<sub>9</sub>(9S3)<sub>0.5</sub>]<sup>2.5−</sup>. Hirshfeld analysis of <b>1</b> and <b>2</b> shows inter-chain contacts are dominated by I<sup>…</sup>I, H<sup>…</sup>I, S<sup>…</sup>H, and S<sup>…</sup>I interactions. The compounds show bandgaps in the range of 2.0–2.3&#xa0;eV and thermally decompose sequentially with the loss of thioalkane, EI<sub>3</sub>, then CuI.</p> Graphical Abstract <p></p>

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Dithiolane and 1,4,7-Trithianonane Complexes of BiI3/CuI and SbI3/CuI

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  • 发表日期：

    2025年11月26日

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  • James H. Ballenger,
  • HongJin Ahn,
  • Pearl Kluger,
  • Todd Reynolds,
  • Aaron D. Nicholas,
  • Robert D. Pike

摘要

Reaction of BiI3/CuI or SbI3/CuI mixtures with the cyclic thioalkanes 1,3-dithiolane (DTL) or 1,4,7-trithiacyclononane (9S3) in toluene yielded the compounds BiCu3I6(DTL)3 (1), SbCu3I6(DTL)3 (2), and Bi2Cu3I9(9S3)4 (3). All compounds were characterized via single crystal X-ray structure determination, powder X-ray diffraction, thermogravimetric analysis, elemental analysis, infrared, and diffuse reflectance spectroscopy. In all cases, sulfur centers bond only to Cu(I). Compounds 1 and 2 consist of isostructural 1D linear chain networks consisting of EI6 octahedra (E = Bi, Sb) in which three mutually cis edges are capped with Cu(I) centers via μ2-I forming an ECu3I6 cluster. All three DTL ligands are bidentate. Two DTL ligands bridge pairs of adjacent copper atoms in the ECu3I6 cluster. Bridging by the remaining DTL links the clusters into infinite chains, …[ECu3I6(DTL)2](DTL)… Compound 3 displays a unique ionic structure, [Cu5(9S3)7]5+[Bi4CuI18(9S3)]5−. The cation is composed of a central 9S3 ligand that bridges disordered duos/trios of [Cu(9S3)]+ units, yielding [Cu2.5(9S3)3.5]2.5+. The anion consists of half-independent face-sharing double octahedron, [Bi2I9]3− in which one of the trio of μ2-I centers further coordinates a half [Cu(9S3)]+ unit, yielding [Bi2Cu0.5I9(9S3)0.5]2.5−. Hirshfeld analysis of 1 and 2 shows inter-chain contacts are dominated by I…I, H…I, S…H, and S…I interactions. The compounds show bandgaps in the range of 2.0–2.3 eV and thermally decompose sequentially with the loss of thioalkane, EI3, then CuI.

Graphical Abstract