Cai Yunhe, Chippindale Ann M, Curry Richard J, Vaqueiro Paz
Department of Chemistry, University of Reading, Whiteknights, Reading, Berkshire RG6 6DX, United Kingdom.
Photon Science Institute, Department of Electrical and Electronic Engineering, University of Manchester, Manchester, M13 9PL, United Kingdom.
Inorg Chem. 2021 Apr 5;60(7):5333-5342. doi: 10.1021/acs.inorgchem.1c00318. Epub 2021 Mar 22.
Hybrid bismuth-containing halides are emerging as alternative candidates to lead-containing perovskites for light-harvesting applications, as Bi is isoelectronic with Pb and the presence of an active lone pair of electrons is expected to result in outstanding charge-carrier transport properties. Here, we report a family of one binary and three ternary iodobismuthates containing 1,4-diazabicyclo[2.2.2]octane (DABCO). These materials have been prepared solvothermally and their crystal structures, thermal stability, and optical properties determined. Reactions carried out in the presence of bismuth iodide and DABCO produced (CHN)BiI (), which consists of hybrid ribbons in which pairs of edge-sharing bismuth octahedra are linked by DABCO ligands. Short I···I contacts give rise to a three-dimensional network. Similar reactions in the presence of copper iodide produced (CHN)BiCuI and (CHN)BiCuI in which either ethylated DABCO cations (EtDABCO) or monoprotonated DABCO cations (DABCOH) are coordinated to copper in discrete tetranuclear and trinuclear clusters, respectively. In the presence of potassium iodide, a unique three-dimensional framework, (CHN)[(CHN)KBiI] , was formed, which contains one-dimensional hexagonal channels approximately 6 Å in diameter. The optical band gaps of these materials, which are semiconductors, range between 1.82 and 2.27 eV, with the lowest values found for the copper-containing discrete clusters. Preliminary results on the preparation of thin films are presented.
含铋混合卤化物正成为用于光捕获应用的含铅钙钛矿的替代候选材料，因为铋与铅是等电子体，并且预计活性孤对电子的存在会导致出色的电荷载流子传输性能。在此，我们报道了一族包含1,4 - 二氮杂双环[2.2.2]辛烷（DABCO）的一种二元和三种三元碘铋酸盐。这些材料已通过溶剂热法制备，并确定了它们的晶体结构、热稳定性和光学性质。在碘化铋和DABCO存在下进行的反应生成了(CHN)BiI ，它由混合带组成，其中成对的边共享铋八面体通过DABCO配体相连。短的I···I接触形成了三维网络。在碘化铜存在下的类似反应生成了(CHN)BiCuI 和(CHN)BiCuI ，其中乙基化的DABCO阳离子（EtDABCO）或单质子化的DABCO阳离子（DABCOH）分别在离散的四核和三核簇中与铜配位。在碘化钾存在下，形成了独特的三维框架(CHN)[(CHN)KBiI] ，它包含直径约为6 Å的一维六边形通道。这些半导体材料 的光学带隙在1.82至2.27 eV之间，含铜离散簇的带隙值最低。本文还给出了薄膜制备的初步结果。
