Investigations of Group 12 (IIB) Metal Halide/Pseudohalide-Bipy Systems:  Syntheses, Structures, Properties, and TDDFT Calculations (Bipy = 2,2‘-bipyridine or 4,4‘-bipyridine)

Abstract

Ten compounds of the IIB metal halide/pseudohalide-bipy system, β-[ZnBr 2 (4,4′-bipy)] n (1), [Cd 2 Br 5 (4,4′-bipyH) 2 ]-(CdBr 3 ) (2), [Cd 3 Br 6 (4,4′-bipy)] n (3), [CdI 2 (4,4′-bipy)] n (4), (HgI 2 ) 2 (4,4′-bipy) (5), [Hg(CN) 2 (4,4′-bipy)(H 2 O) 2 ] n (6), HgCl 2 (2,2′bipy) (7), [HgCl 2 (2,2′-bipy)]‚2HgCl 2 (8), [Hg 3 Br 6 (2,2′-bipy)]‚HgBr 2 (9), and [HgI 2 (2,2′-bipy)]‚HgI 2 (10), have been synthesized via hydro(solvo)thermal and solid-state reactions; except for 4, all the other compounds are reported for the first time. Compound 1 features a 1-D zigzag chain, based on tetrahedral zinc atoms bridged by 4,4′-bipy molecules and terminally coordinated by two bromine atoms. The chains are linked by hydrogen bonds and π‚‚‚π interactions to form a 2-D sheet. Compound 2 possesses dinuclear [Cd 2 Br 5 (4,4′-bipyH) 2 ] + cations and CdBr 3anions. Compound 3 has a 2-D layered structure, constructed from novel triple chains and bridging 4,4′-bipy ligands. The triple chains contain edge-shared CdBr 6 and CdBr 5 N octahedra. In 4, the layers are formed by monochains and bridging 4,4′-bipy molecules. The monochains contain edge-shared CdI 4 N 2 octahedra. Compound 5 features a discrete structure with a 4,4′-bipy ligand bridging two HgI 2 moieties. Compound 6 has a 1-D zigzag chain, containing octahedral mercury atoms and bridging 4,4′-bipy molecules. In 7 and 8, mercury atoms are tetrahedrally coordinated to two chlorine atoms and two nitrogen atoms. In 9, 2-, 3-, 4-, and 5-coordinated mercury atoms coexist, whereas in 10, the mercury atoms are only 2-and 4-coordinated. Photoluminescence investigations reveal that the compounds display strong emissions in the blue/green/yellow regions, which, in combination with the molecular orbital (MO) calculations of 1, 5, and 7, leads us to conclude that the emissions originate from a ligand-to-ligand charge-transfer (LLCT) transition. The solid-state diffuse reflectance spectra, IR, and TG-DTA are also presented.

Crystal structure of 2,2’-bipyridindiium (2,2’-bipyridyl-κ2N,N’)- tetrabromidorhodate(III) bromide, (C10H10N2)[RhBr4(C10H8N2)]Br, C20H18Br5N4Rh

“…Among them the particularly important role is played by 4,4'-and 2,2'-bipyridines that belong to the most frequently used oligopyridine organic components in crystal engineering of inorganic-organic hybrids [1,2]. We have recently reported structural, spectroscopic and thermoanalytical properties of the hybrid material [4,4' ,astrategythatwas successfully applied before using flexible a,w-diammonio ions of medium chain lengthso rs emiflexible 1,4-diazoniacycloheptane ions [4][5][6].…”

Crystal structure of (2,2'-bipyridine-k2:N1:N2)-bis(4-acetamidobenzoato-k2:O:O2)copper(II) hydrate, Cu(C10H8N2)(C9H8NO3)2 · 2.43H2O

“…Inorganic-organic hybrid materials are of great interest because of their intriguing structural features and potential in various applications, such as electrical conductivity, photochemistry, ion exchange, catalysis, biochemistry, and nonlinear optical behavior [1][2][3]. Al arge variety of ligands containing bridging functionalities such as carboxylates, phosphonates, 4,4'-bipy, and 2,2'-bipy have been exploited to prepare new inorganic-organic hybrid materials [4].…”

Synthesis, Structures, and Properties of Four Novel HgII Complexes Based on Pyridine Acylamide Ligands

“…Single crystal X-ray diffraction reveals that compound 4 crystallises in the chiral P4 3 2 1 2 space group with a Flack factor of 0.011 (8). Notably, this kind of chirality should be derived from spontaneous resolution.…”

“…In addition, the assembly of supramolecular networks containing pyridine acylamide ligands organised through hydrogen bonds has also attracted much attention, which can be used as a driving force to give interesting nanotubes or zeolitelike frameworks through inter-ring or inter-tube hydrogen bonding. [7][8][9][10][11][12] Herein, we synthesised four novel complexes based on pyridine acylamide ligands. Their syntheses, structures, and photoluminescence properties are discussed.…”