Hybrid iodoplumbates with metal complexes: syntheses, crystal structures, band gaps and photoelectric properties

Bo Zhang; Hai-Yan Sun; Jun Li; Ya-Ru Xu; Yu-Ping Xu; Xue Yang; Guo-Dong Zou

doi:10.1039/c9dt04756e

Hybrid iodoplumbates with metal complexes: syntheses, crystal structures, band gaps and photoelectric properties

Dalton Trans. 2020 Feb 14;49(6):1803-1810. doi: 10.1039/c9dt04756e. Epub 2020 Jan 28.

Authors

Bo Zhang¹, Hai-Yan Sun², Jun Li¹, Ya-Ru Xu³, Yu-Ping Xu³, Xue Yang³, Guo-Dong Zou⁴

Affiliations

¹ College of Chemistry and Chemical Engineering, Shandong Provincial Key Laboratory and Collaborative Innovation Center of Chemical Energy Storage & Novel Cell Technology, Liaocheng University, Shandong, Liaocheng 252059, People's Republic of China. bzhang@lcu.edu.cn junli@lcu.edu.cn and State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China.
² State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China.
³ College of Chemistry and Chemical Engineering, Shandong Provincial Key Laboratory and Collaborative Innovation Center of Chemical Energy Storage & Novel Cell Technology, Liaocheng University, Shandong, Liaocheng 252059, People's Republic of China. bzhang@lcu.edu.cn junli@lcu.edu.cn.
⁴ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China and College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang, Henan 464000, People's Republic of China.

PMID: 31989138
DOI: 10.1039/c9dt04756e

Abstract

With the in situ-generated [Pb(MCP)₄]²⁺ (HMCP⁺ = 1-methyl-4-(carboxyl)pyridinium) or [M(phen)₃]²⁺ (M = Co, Fe and Ni; phen = 1,10-phenanthroline) complexes as structural directing agents and charge-balancing ions, we solvothermally synthesized and structurally characterized four new organic-inorganic hybrid iodoplumbates. Compound K₂[Pb(MCP)₄]Pb₃I₁₀ (1) represents the first K⁺ and [Pb(MCP)₄]²⁺ co-templated hybrid haloplumbate, and exhibits a curve-like anionic layer of [Pb₃I₁₀]_n^4n-. Compounds [M(phen)₃]Pb₂I₆·CH₃CN (M = Co (2), Fe (3) and Ni (4)) have isostructural phases, and feature a one-dimensional (1D) [Pb₂I₆]_n^2n- anionic chain characteristic of pyramid-like [PbI₅] units. The optical property studies show that compounds 1-4 exhibit semiconductor behaviors with the band gaps of 1.98-2.68 eV. In addition, the title compounds exhibited interesting photoelectrical responsive properties, with the photocurrent density in the order of 1 > 3 > 2 > 4. The thermal stabilities of the title compounds 1-4, as well as the theoretical band structure and density of states (DOS) of compounds 1 and 2 have also been studied.