Synthesis, Crystal, and Electronic Structure of (HpipeH2)2[Sb2I10](I2), with I2 Molecules Linking Sb2X10 Dimers into a Polymeric Anion: A Strategy for Optimizing a Hybrid Compound’s Band Gap

Abstract

In searching for a tool for optimizing the band gap of a hybrid compound capable of serving as a light-harvesting material in lead-free photovoltaics, we synthesized a new polyiodoantimonate (HpipeH2)2[Sb2I10](I2) and analyzed its crystal and electronic structure by application of X-ray crystal structure analysis, Raman and diffuse reflectance spectroscopies, and quantum chemical calculations. It was demonstrated that I2 molecules link Sb2I10 edge-sharing octahedra into zig-zag chains, whereas the organic cations link inorganic anionic chains into a 3D structure featuring a complex pattern of covalent bonds and non-covalent interactions. Overall, these features provide the background for forming the electronic structure with a narrow band gap of 1.41 eV, therefore being a versatile tool for optimizing the band gap of a potential light-harvesting hybrid compound.

Polymeric polyiodo-chlorotellurates(iv): new supramolecular hybrids in halometalate chemistry

“…All five compounds were prepared via the approach commonly used for the syntheses of Te, 40,55 Bi, 41,43 and Sb (ref. 56 and 75) polyhalogen-halometalates in aqueous solutions of hydrohalic acids. Because I 2 has poor solubility in concentrated HCl, CH 3 CN was added in the synthesis of 1 .…”

“…84 Thus, the diiodine molecules were less elongated than those in the previously reported polyiodo-iodometalates. 41,43,75,85–89 However, a structurally similar series of polyiodo-bromotellurates Cat 2 {[TeBr 6 ](I 2 )} also showed little to no I–I bond elongation along with I 2 vibration modes above 180 cm −1 in all compounds except one. 40…”

4,5-Diiodo-1-H-imidazole-derived linker ligand and Cu(i) and Co(ii) coordination polymers based thereupon

“…There are several types of "building blocks" which are especially common for the design of XB-based architectures. These include perfluoromonoiodo-and diiodoarenes, [20][21][22][23][24][25] hypervalent iodine derivatives, [26][27][28] polyhalogens, [29][30][31][32][33][34][35] etc. ; the search for novel synthons is ongoing.…”

A Comprehensive Investigation into the Crystallology, Molecule, and Quantum Chemistry Properties of Two New Hydrous Long-Chain Dibasic Ammonium Salts CnH2n+8N2O6 (n = 35 and 37)

“…However, the synthesis of long-chain binary ammonium salts with 1,3-propanediamine and long-chain fatty acids as ligands has not been reported. The study of binary ammonium salt by quantum chemical calculation [ 42 , 43 , 44 , 45 ] has never been reported.…”