Abstract

In recent years, attributed to their excellent anionic structure diversity, halogenobismuthate(III) materials have been a popular research direction. Apart from their interesting structural motifs, such hybrids often demonstrate potentially valuable properties such as luminescence and optoelectronics. Herein, we report the study of the first chlorobismuthate(III) hybrid compound involving discrete binuclear Bi₂Cl₁₁ and mononuclear BiCl₆ anions coexisting together in the same structure. The anionic framework is connected to water molecules by O–H···Cl hydrogen bonds to build a corrugate chain spreading in the (111) direction. The intermolecular interactions were examined using Hirshfeld surfaces. The vibrational properties were investigated using the IR absorption spectroscopy. The optical study revealed the absorption and photoluminescence properties of the compound. Theoretical investigations were undertaken by means of DFT and TDDFT calculations on a suitably chosen cluster. A good agreement was found between calculations and experimental results leading to consistent vibrational and optical features assignments. The thermal behaviour was discussed. The variation of the dielectric loss log(ɛ″) with log(ω) was found to follow the empirical law, ɛ″ = Bωm(T). The dependence of the exponent m(T) on temperature, suggested that the correlated barrier hopping “CBH” and the non-overlapping small polaron tunneling “NSPT” are the appropriate models for the conduction mechanism.

Graphic Abstract

摘要

近年来，由于其优异的阴离子结构多样性，卤化铋（III）材料已成为受欢迎的研究方向。除了它们有趣的结构图案外，此类杂种还经常表现出潜在的有价值的特性，例如发光和光电。在这里，我们报告的研究涉及离散双核Bi ₂ Cl ₁₁和单核BiCl ₆的第一个氯铋（III）杂化化合物。阴离子以相同的结构共存。阴离子骨架通过O·H···Cl氢键与水分子连接，从而形成沿（111）方向扩展的波纹链。使用Hirshfeld表面检查分子间的相互作用。使用红外吸收光谱研究了振动特性。光学研究揭示了该化合物的吸收和光致发光性质。理论研究通过DFT的装置和TDDFT计算适当选择的群集上进行。在计算和实验结果之间找到了很好的一致性，从而导致了一致的振动和光学特征分配。讨论了热行为。发现介电损耗log（ɛ''）与log（ω）的变化遵循经验定律，ɛ''=Bωm（T）。

图形摘要