2, 2′-Bipyridyl-1, 1′-dioxide based bismuth(iii) bromide hybrids: studies on crystal structure and luminescence. Issue 20 (7th May 2021)

• Record Type: Journal Article
• Authors: Jin, Jian-Ce; Lin, Yang-Peng; Lin, Li-Fang; Xiao, Cao; Song, Ying; Shen, Nan-Nan; Gong, Liao-Kuo; Zhang, Zhi-Zhuan; Du, Ke-Zhao; Huang, Xiao-Ying
• Is Part Of: CrystEngComm. Volume 23:Issue 20(2021)
• Page Start: 3744
• Page End: 3752
• Publication Date: 2021-05-07
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/d1ce00362c
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : The choice of organic solvents could induce inorganic–organic bromobismuthate hybrids with diverse metal–ligand linking modes. Abstract : Three bismuth(iii ) bromide hybrids based on 2, 2′-bipyridyl-1, 1′-dioxide (bp2do) were obtained by a solvothermal method, namely Bi2 Br6 (bp2do)2 (1 ), Bi2 Br6 (bp2do)2 ·0.5CH3 CN (2 ), and [PP14][BiBr4 (bp2do)] (3, PP14 = 1-butyl-1-methylpiperidinium). 1 features a centrosymmetric [Bi2 Br6 O4 ] dimer, in which two identical [BiBr4 O2 ] octahedra edge-share two Br atoms; 2 contains a [Bi2 Br6 O4 ] dinuclear unit with a unique configuration, in which a [BiBr4 O2 ] octahedron face-shares one Br and two O atoms with a [BiBr3 O4 ] pentagonal-bipyramid. Moreover, the metal–ligand linking mode adopted in 2 has not been reported before. The choice of organic solvents could induce different Bi–Br–bp2do geometries with a dimer in 1 and a dinuclear unit in 2 . Introduction of ionic liquid cations resulted in the ionic compound 3 featuring a mononuclear [BiBr4 (bp2do)] unit. A more rigid environment with more hydrogen bonds leads to visible green phosphorescence with long lifetime for 3 under UV light. The three compounds possess similar phosphorescence peaks at 77 K, which originates from inorganic-to-organic charge transfer (IOCT) as confirmed by density functional theory (DFT) calculations.