Four Discrete Silver Iodobismuthates/Bromobismuthates with Metal Complexes: Syntheses, Structures, Photocurrent Responses, and Theoretical Studies

Bo Zhang; Jun Li; Ming Pang; Ying-Shuo Wang; Meng-Zhen Liu; Hui-Meng Zhao

doi:10.1021/acs.inorgchem.1c03026

Four Discrete Silver Iodobismuthates/Bromobismuthates with Metal Complexes: Syntheses, Structures, Photocurrent Responses, and Theoretical Studies

Inorg Chem. 2022 Jan 10;61(1):406-413. doi: 10.1021/acs.inorgchem.1c03026. Epub 2021 Dec 21.

Authors

Bo Zhang^{1

2}, Jun Li^{1

2}, Ming Pang¹, Ying-Shuo Wang¹, Meng-Zhen Liu¹, Hui-Meng Zhao¹

Affiliations

¹ College of Chemistry and Chemical Engineering, Liaocheng University, Shandong, Liaocheng 252059, China.
² State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou 350002, China.

PMID: 34931819
DOI: 10.1021/acs.inorgchem.1c03026

Abstract

Using in situ formed metal complexes of [Fe(bipy)₃]²⁺ or [Ni(bipy)₃]²⁺ (bipy = 2,2'-bipyridine) as templates, four new Ag-Bi-X (X = I and Br) compounds are first isolated in the metal-complex-decorated heterometallic halobismuthate family, namely [M(bipy)₃]AgBiI₆ (M = Fe (1), Ni (2)), [Fe(bipy)₃]AgBiBr₆ (3), and [Ni(bipy)₃]AgBiBr₆ (4). Compounds 1-4 feature discrete [AgBiX₆]_n^2n- anions, exhibiting three polymorphisms that may be ascribed to the different stackings and the flexible condensations of [BiX₆] octahedrons and [AgX₄] tetrahedra/[AgX₃] triangles. UV-vis diffuse reflectance analyses reveal that they are narrow band gap semiconductor materials (ca. 1.82-2.13 eV). Intriguingly, the title compounds display excellent photoelectrical switching properties, with photocurrent density following the order 3 > 4 > 2 > 1. In addition, the comparative studies of intermolecular interactions, theoretical band structures, density of states, and effective masses of three polymorphisms have also been investigated.