Wenxiang Chai

Preparation of Porous Three‐Dimensional Quaternary Thioantimonates(III) ACuSb2S4 (A=Rb, Cs) through a Surfactant‐Thermal Method

Two novel porous three-dimensional (3D) quaternary thioantimonates(III) ACuSb2S4 (A = Rb, Cs) were successfully synthesized by employing the neutral surfactant PEG-400 (PEG = polyethyleneglycol) as reaction media, these are significantly different from the known quaternary A-Cu-Sb-S thioantimonates(III) with two-dimensional (2D) crystal structures. This is the first time that crystalline quaternary chalcogenides have been prepared in surfactant media. Both experimental and theoretical studies confirm they are semiconductors with narrow band gaps. Our results demonstrated that the surfactant-thermal strategy could offer a new opportunity to explore novel chalcogenides with diverse crystal structures and interesting physicochemical properties.

A double salt of iodo­bis­muthate: cis-aqua­iodidobis(1,10-phenanthroline)cobalt(II) tris­(1,10-phenanthroline)cobalt(II) trans-hexa-μ2-iodido-hexa­iodidotribismuthate(III)

In the title complex, [Co(C12H8N2)3][CoI(C12H8N2)2(H2O)][Bi3I12], conventionally abbreviated [Co(phen)3][CoI(phen)2(H2O)][Bi3I12], where phen is 1,10-phenanthroline, the CoII atom in one cation is coordinated by six N atoms from three phen ligands in an octahedral coordination while the CoII atom in the other cation is coordinated octahedrally by four N atoms from two phen ligands, one water O atom and one I atom. In the anion, three BiIII ions adopt an octahedral coordination constructed by six I− ligands. The three BiI6 octahedra are fused together through trans face-sharing.

Facile Hydrazine‐Hydrothermal Syntheses and Characterizations of Two New Quaternary Thioarsenates (III): Two‐Dimensional SrAg4As2S6*2H2O and One‐Dimensional BaAgAsS3

Two new quaternary thioarsenates(III), SrAg4 As2 S6 ⋅2 H2 O (1) and BaAgAsS3 (2), have been prepared through a hydrazine-hydrothermal method at low temperature. Compound 1 possesses a two-dimensional (2D) layer network, while compound 2 features a one-dimensional (1D) column structure. The detailed structure analysis indicates that Sr(2+) and Ba(2+) cations have different directing effects on the structures of thioarsenates(III). Both experimental and theoretical studies demonstrate that compounds 1 and 2 are narrow-gap semiconductors. Our success in synthesizing these two quaternary thioarsenates(III) proves that the hydrazine-hydrothermal technique is a powerful yet facile synthetic method for exploring new complex chalcogenides with diverse crystal structures and interesting physical properties.

A square-pyramidal copper(II) complex with strong intramolecular hydrogen bonds: diaqua(N,N'-dimethylformamide-κO)bis[2-(diphenylphosphoryl)benzoato-κO]copper(II).

In the title Cu(II) complex, [Cu(C19H14O3P)2(C3H7NO)(H2O)2], the molecule is bisected by a twofold axis relating the two 2-(diphenylphosphoryl)benzoate (ODPPB) ligands. The asymmetric unit consists of a Cu(II) metal centre on the symmetry axis, an ODPPB ligand, one water ligand and one dimethylformamide (DMF) ligand (disordered around the twofold axis). The Cu(II) ion has fivefold coordination provided by two carboxylate O atoms from two ODPPB ligands, two O atoms from two coordinated water molecules and another O atom from a (disordered) DMF molecule, giving a CuO5 square-pyramidal coordination geometry. The ODPPB ligand adopts a terminal monocoordinated mode with two free O atoms forming two strong intramolecular hydrogen bonds with the coordinated water molecules, which may play a key role in the stability of the molecular structure, as shown by the higher release temperature for the coordinated water molecules than for the coordinated DMF molecule. The optical absorption properties of powder samples of the title compound have also been studied.

Aqua­[4-(hy­droxy­imino­meth­yl)pyridine-κN 1](imino­diacetato-κ3 O,N,O′)copper(II)

In the title complex, [Cu(C4H5NO4)(C6H6N2O)(H2O)], conventionally abbreviated Cu(IDA)(4-OXPy)(H2O), where IDA is iminodiacetate and 4-OXPy is 4-(hydroxyiminomethyl)pyridine, the CuII atom exhibits a distorted square-pyramidal coordination geometry, which is constructed from two O atoms and one N atom from a IDA ligand, one N atom from 4-OXPy ligand and one O atom from water. This molecule looks like a space shuttle, the IDA ligand is its empennage (tail), and the 4-OXPy ligand is its airframe. The complexes are linked into two-dimensional supramolecular layers parallel to (100) by three pairs of O—H⋯O hydrogen bonds. Two pairs of N—H⋯O hydrogen bonds further connect these supramolecular layers, forming a three-dimensional supramolecular network.

Facile preparation of a three-coordinate copper(I) complex: Steric hindrance, supramolecular structure, optical property and TD-DFT study

GRAPHICAL ABSTRACT ABSTRACT The solution reaction of Cu(CH3CN)4(PF6) with a NN ligand 2-(2′-quinolyl)benzimidazole and a sterically bulky P ligand tris(2-methylphenyl)phosphine facilely yielded the three-coordinate copper(I) complex [Cu(2-QBI)(o-Tol3P)](PF6) (1). The complex has been characterized by single-crystal X-ray diffraction, Fourier Transform infrared spectroscopy and elemental analysis, UV–Vis (ultraviolet–visible) and photoluminescent spectroscopy studies. Time-dependent density functional theory has been used for calculating the electronic origin of the low-lying excited states, which were unexpectedly assigned mainly as a ligand-to-ligand or an intra-ligand charge transfer state instead of the metal-to-ligand charge transfer transition. Interestingly, 1 exhibits a concentration-dependent absorption in solution. This absorption behavior is interpreted as some excimers formation based on the study of supramolecular structure, spectroscopy and calculations.

catena-Poly[[(1,10-phenanthroline-κN,N')copper(I)]-μ(2)-iodido].

The solvothermal reaction of copper(I) iodide and 1,10-phenanthroline (phen) in ethanol yielded the title polymeric compound, [CuI(C12H8N2)]n. The asymmmetric unit comprises one Cu+ cation, one I− anion and one phen ligand. Each Cu+ cation is in a distorted tetrahedral coordination by two iodide anions and two N atoms from a bidentate chelating phen ligand. The Cu+ cations are bridged through the iodide anions, leading to a zigzag chain structure extending parallel to [100]. There are π–π interactions among adjacent phen ligands of one chain [centroid–centroid distance = 3.693 (3) Å].

rac-2,2′-Bis(diphenyl­phosphan­yl)-1,1′-binaphth­yl: a racemic diphosphine ligand

The asymmetric unit of the title compound, C44H32P2, conventionally abbreviated BINAP, is one half of the complete chiral BINAP molecule, which adopts a C2 crystallographic point-group symmetry with a twofold axis splitting the molecule in two identical halves; a center of symmetry between molecules further determines the racemic pairs. There are no obvious supramolecular interactions between adjacent BINAP molecules.

A new potential NLO compound with a supramolecular layered structure: aqua(hexamethylenetetramine-κN)(iminodiacetato-κ3O,N,O')copper(II).

In the noncentrosymmetric title compound, [Cu(C(4)H(5)NO(4))(C(6)H(12)N(4))(H(2)O)] or [Cu(IDA)(HMTA)(H(2)O)], where IDA is iminodiacetate and HMTA is hexamethylenetetramine, the asymmetric unit consists of a whole mononuclear neutral molecule, where the Cu(II) cation is coordinated by two carboxylate O atoms and one N atom from the IDA ligand, by one N atom from the HMTA ligand and by the O atom of the coordinated water molecule, giving rise to a CuN(2)O(3) distorted square-pyramidal coordination geometry. The IDA and HTMA ligands adopt terminal tri- and monocoordinated modes, respectively. All adjacent molecules within the ac plane are connected to each other via two pairs of O-H···O and one N-H...O hydrogen bond, forming a (4,4) supramolecular two-dimensional network. In the unit cell, these layers stack alternately in an …ABABAB… sequence along the b axis. The optical absorption properties of this compound have been studied on powder samples, which had previously been examined by powder X-ray diffraction.

Chloridobis(1,10-phenanthroline)zinc(II) tetra­chlorido(1,10-phenan­throline)bis­muthate(III) monohydrate

In the crystal structure of the title monohydrate salt, [ZnCl(C12H8N2)2][BiCl4(C12H8N2)]·H2O, the ionic components are linked into three-dimensional supramolecular channels by five pairs of C—H⋯Cl hydrogen bonds and π–π stacking interactions with an interplanar distance of 3.643 (2) Å. The solvent water molecules are lodged in the channels.