(Chlorido/bromido)[(1,2,5,6-η)-cycloocta-1,5-diene](4-isopropyl-1-methyl-1,2,4-triazol-5-ylidene)rhodium(I)

A new triazole-based neutral RhI complex, [Rh(Cl0.846Br0.154)(C6H11N3)(C8H12)], has been synthesized and structurally characterized. The RhI atom has a distorted square-planar coordination environment, formed by a bidentate cycloocta-1,5-diene (COD) ligand, an N-heterocyclic carbene and a halide ligand that shows substitutional disorder (Cl:Br = 0.846:0.154). No significant intermolecular interactions other than van der Waals forces are found in the crystal structure. Diffraction data indicated a two-component inversion twin with a ratio of 0.95 (5):0.05 (5).

Halobismuth(III) salts with substituted aminopyridinium cations

The crystal structures of six halobismuth(III) salts of variously substituted aminopyridinium cations display discrete mononuclear [BiCl6]3− and dinuclear [Bi2 X 10]4− anions (X = Cl or Br), and polymeric cis-double-halo-bridged [Bi nX 4 n ] n− anionic chains (X = Br or I). Bis(2-amino-3-ammoniopyridinium) hexachloridobismuth(III) chloride monohydrate, (C5H9N3)2[BiCl6]Cl·H2O, (1), contains discrete mononuclear [BiCl6]3− and chloride anions. Tetrakis(2-amino-3-methylpyridinium) di-μ-chlorido-bis[tetrachloridobismuth(III)], (C6H9N2)4[Bi2Cl10], (2), tetrakis(2-amino-3-methylpyridinium) di-μ-bromido-bis[tetrabromidobismuth(III)], (C6H9N2)4[Bi2Br10], (3), and bis(4-amino-3-ammoniopyridinium) di-μ-chlorido-bis[tetrachloridobismuth(III)] dihydrate, (C5H9N3)2[Bi2Cl10]·2H2O, (4), incorporate discrete [Bi2 X 10]4− anions (X = Cl or Br), while catena-poly[2,6-diaminopyridinium [[cis-diiodidobismuth(III)]-di-μ-iodido]], {(C5H8N3)[BiI4]} n , (5), and catena-poly[2,6-diaminopyridinium [[cis-dibromidobismuth(III)]-di-μ-bromido]], {(C5H7N2)[BiBr4]} n , (6), include [Bi nX 4 n ] n− anionic chains (X = Br or I). Structures (2) and (3) are isostructural, while that of (5) is a pseudomerohedral twin. There is no discernible correlation between the type of anionic species obtained and the cation or halide ligand used. The BiIII centres always have a slightly distorted octahedral geometry and there is a correlation between the Bi—X bond lengths and the number of classic N—H...X hydrogen bonds that the X ligand accepts, with a greater number of interactions corresponding with slightly longer Bi—X distances. The supramolecular networks formed by classic N—H...X hydrogen bonds include ladders, bilayers and three-dimensional frameworks.

Hydroiodic Acid Additive Enhanced the Performance and Stability of PbS-QDs Solar Cells via Suppressing Hydroxyl Ligand

The recent emerging progress of quantum dot ink (QD-ink) has overcome the complexity of multiple-step colloidal QD (CQD) film preparation and pronouncedly promoted the device performance. However, the detrimental hydroxyl (OH) ligands induced from synthesis procedure have not been completely removed. Here, a halide ligand additive strategy was devised to optimize QD-ink process. It simultaneously reduced sub-bandgap states and converted them into iodide-passivated surface, which increase carrier mobility of the QDs films and achieve thicker absorber with improved performances. The corresponding power conversion efficiency of this optimized device reached 10.78%. (The control device was 9.56%.) Therefore, this stratege can support as a candidate strategy to solve the QD original limitation caused by hydroxyl ligands, which is also compatible with other CQD-based optoelectronic devices.

Intermolecular hydrogen bonding in isostructural pincer complexes [OH-( t-BuPOCOP t-Bu)MCl] (M = Pd and Pt)

In the crystal structure of the isostructural title compounds, namely {2,6-bis[(di-tert-butylphosphanyl)oxy]-4-hydroxyphenyl}chloridopalladium(II), [Pd(C22H39O3P2)Cl], 1, and {2,6-bis[(di-tert-butylphosphanyl)oxy]-4-hydroxyphenyl}chloridoplatinum(II), [Pt(C22H39O3P2)Cl], 2, the metal centres are coordinated in a distorted square-planar fashion by the POCOP pincer fragment and the chloride ligand. Both complexes form strong hydrogen-bonded chain structures through an interaction of the OH group in the 4-position of the aromatic POCOP backbone with the halide ligand.

Three zinc iodide complexes based on phosphane ligands: syntheses, structures, optical properties and TD–DFT calculations

Three zinc iodide complexes based on phosphane ligands, namely diiodidobis(triphenylphosphane-κP)zinc(II), [ZnI2(C18H15P2)2], (1), diiodidobis[tris(4-methylphenyl)phosphane-κP]zinc(II), [ZnI2(C21H21P2)2], (2), and [bis(diphenylphosphoryl)methane-κ2O,O′]zinc(II) tetraiodidozinc(II), [Zn(C25H22O2P2)3][ZnI4], (3), have been synthesized and characterized. Single-crystal X-ray diffraction revealed that the structures of (1) and (2) are both mononuclear four-coordinated ZnI2complexes containing two monodentate phosphane ligands, respectively. Surprisingly, (2) spontaneously forms an acentric structure, suggesting it might be a potential second-order NLO material. The crystal structure of complex (3) is composed of two parts, namely a [Zn(dppmO2)3]2+cation [dppmO2is bis(diphenylphosphoryl)methane] and a [ZnI4]2−anion. The UV–Vis absorption spectra, thermal stabilities and photoluminescence spectra of the title complexes have also been studied. Time-dependent density functional theory (TD–DFT) calculations reveal that the low-energy UV absorption and the corresponding light emission both result from halide-ligand charge-transfer (XLCT) excited states.

Halide and substituent dependent structural variation in copper(i) halide complexes of 1,5,9-triphosphacyclododecanes

Mono- or dimeric structures of Cu(i) complexes of 12aneP3 macrocycles are obtained depending on the nature of the secondary halide ligand.

N—H...X (X = Cl and Br) hydrogen bonds in three isomorphous 3,5-dichloropyridinium salts

Specific short contacts are important in crystal engineering. Hydrogen bonds have been particularly successful and together with halogen bonds can be useful for assembling small molecules or ions into crystals. The ionic constituents in the isomorphous 3,5-dichloropyridinium (3,5-diClPy) tetrahalometallates 3,5-dichloropyridinium tetrachloridozincate(II), (C5H4Cl2N)2[ZnCl4] or (3,5-diClPy)2ZnCl4, 3,5-dichloropyridinium tetrabromidozincate(II), (C5H4Cl2N)2[ZnBr4] or (3,5-diClPy)2ZnBr4, and 3,5-dichloropyridinium tetrabromidocobaltate(II), (C5H4Cl2N)2[CoBr4] or (3,5-diClPy)2CoBr4, arrange according to favourable electrostatic interactions. Cations are preferably surrounded by anions and vice versa; rare cation–cation contacts are associated with an antiparallel dipole orientation. N—H...X (X = Cl and Br) hydrogen bonds and X...X halogen bonds compete as closest contacts between neighbouring residues. The former dominate in the title compounds; the four symmetrically independent pyridinium N—H groups in each compound act as donors in charge-assisted hydrogen bonds, with halogen ligands and the tetrahedral metallate anions as acceptors. The M—X coordinative bonds in the latter are significantly longer if the halide ligand is engaged in a classical X...H—N hydrogen bond. In all three solids, triangular halogen-bond interactions are observed. They might contribute to the stabilization of the structures, but even the shortest interhalogen contacts are only slightly shorter than the sum of the van der Waals radii.

Crystal structures offac-tricarbonylchlorido(6,6′-dihydroxy-2,2′-bipyridine)rhenium(I) tetrahydrofuran monosolvate andfac-bromidotricarbonyl(6,6′-dihydroxy-2,2′-bipyridine)manganese(I) tetrahydrofuran monosolvate

The structures of two facially coordinated Group VII metal complexes,fac-[ReCl(C10H8N2O2)(CO)3]·C4H8O (I·THF) andfac-[MnBr(C10H8N2O2)(CO)3]·C4H8O (II·THF), are reported. In both complexes, the metal ion is coordinated by three carbonyl ligands, a halide ligand, and a 6,6′-dihydroxy-2,2′-bipyridine ligand in a distorted octahedral geometry. Both complexes co-crystallize with a non-coordinating tetrahydrofuran (THF) solvent molecule and exhibit intermolecular but not intramolecular hydrogen bonding. In both crystal structures, chains of complexes are formed due to intermolecular hydrogen bonding between a hydroxy group from the 6,6′-dihydroxy-2,2′-bipyridine ligand and the halide ligand from a neighboring complex. The THF molecule is hydrogen bonded to the remaining hydroxy group.