Four mononuclear Cu(i)-halide complexes containing phosphines and pyridine ligands with strong electron donor substituents, [CuCl(PPh)(4-NMepy)] (1), [CuI(PPh)(4-NHpy)] (2), [CuI(POP)(4-NHpy)] (3), and [CuI(POP)(4-NMepy)]·0.5(EtO) (4), (PPh = triphenylphosphine, 4-NMepy = 4-(dimethylamino)pyridine, POP = bis[(2-diphenyl-phosphino)phenyl]ether, 4-NHpy = 4-aminopyridine, EtO = diethyl ether) were synthesized and studied with regard to their structural, photophysical properties and theoretical calculations. The complexes exhibit pure blue thermally activated delayed fluorescence (λ = 442 (1), 436 (2), 464 (3), and 448 nm (4)) in crystalline at room temperature. Emission lifetime analyses and density functional theory (DFT) calculations show that the blue-light emission at room temperature is the singlet (metal + halide)-to-ligand charge transfer state, ((M + X)LCT), while that at 77 K is the state of (M + X)LCT transition character, owing to the small singlet-triplet energy gaps (ΔE = 660-1680 cm). X-ray diffraction structure analysis, photophysical studies and theoretical calculations suggest that the much larger torsion angle between the N-heterocyclic rings and N-Cu-X planes of complex 3 than that of 1, 2 and 4 might causes the bathochromic shift of luminescence, although these complexes containing similar heterocycle ligands.

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The title compound, {[Ag(C6H7AsNO3)(C18H15P)]·H2O}n, has been synthesized from the reaction of 4-aminophenylarsonic acid with silver nitrate, in aqueous ammonia, with the addition of triphenylphosphane (PPh3). The Ag(I) centre is four-coordinated by one amino N atom, one PPh3 P atom and two arsonate O atoms, forming a severely distorted [AgNPO2] tetrahedron. Two Ag(I)-centred tetrahedra are held together to produce a dinuclear [Ag2O2N2P2] unit by sharing an O-O edge. 4-Aminophenylarsonate (Hapa(-)) adopts a μ3-κ(3)N:O:O-tridentate coordination mode connecting two dinuclear units, resulting in a neutral [Ag(Hapa)(PPh3)]n layer lying parallel to the (101̄) plane. The PPh3 ligands are suspended on both sides of the [Ag(Hapa)(PPh3)]n layer, displaying up and down orientations. There is an R2(2)(8) hydrogen-bonded dimer involving two arsonate groups from two Hapa(-) ligands related by a centre of inversion. Additionally, there are hydrogen-bonding interactions involving the solvent water molecules and the arsonate and amine groups of the Hapa(-) ligands, and weak π-π stacking interactions within the [Ag(Hapa)(PPh3)]n layer. These two-dimensional layers are further assembled by weak van der Waals interactions to form the final architecture.

The title compound, {[Zn4(C8H4O4)3(OH)2(C12H6N2O2)2]·2H2O}n, has been prepared hydrothermally by the reaction of Zn(NO3)2·6H2O with benzene-1,4-dicarboxylic acid (H2bdc) and 1,10-phenanthroline-5,6-dione (pdon) in H2O. In the crystal structure, a tetranuclear Zn4(OH)2 fragment is located on a crystallographic inversion centre which relates two subunits, each containing a [ZnN2O4] octahedron and a [ZnO4] tetrahedron bridged by a μ3-OH group. The pdon ligand chelates to zinc through its two N atoms to form part of the [ZnN2O4] octahedron. The two crystallographically independent bdc(2-) ligands are fully deprotonated and adopt μ3-κO:κO':κO'' and μ4-κO:κO':κO'':κO''' coordination modes, bridging three or four Zn(II) cations, respectively, from two Zn4(OH)2 units. The Zn4(OH)2 fragment connects six neighbouring tetranuclear units through four μ3-bdc(2-) and two μ4-bdc(2-) ligands, forming a three-dimensional framework with uninodal 6-connected α-Po topology, in which the tetranuclear Zn4(OH)2 units are considered as 6-connected nodes and the bdc(2-) ligands act as linkers. The uncoordinated water molecules are located on opposite sides of the Zn4(OH)2 unit and are connected to it through hydrogen-bonding interactions involving hydroxide and carboxylate groups. The structure is further stabilized by extensive π-π interactions between the pdon and μ4-bdc(2-) ligands.