Intense photo- and tribo-luminescence of three tetrahedral manganese(II) dihalides with chelating bidentate phosphine oxide ligand.

Three air-stable tetrahedral manganese(ii) dihalide complexes [MnX2(DPEPO)] (DPEPO = bis[2-(diphenylphosphino)phenyl]ether oxide; X = Cl, Br and I) were prepared. All of the obtained compounds were structurally characterized by single-crystal X-ray diffraction analyses, which reveal that they crystallize in centrosymmetric space groups and feature an isolated mononuclear structure with Mn(2+) in a tetrahedral environment. Interestingly, these complexes show excellent photoluminescent performance in neat solid form, with the highest total quantum yield (Φtotal) of up to 70% recorded for the dibromide complex. Intense green flashes of light could be observed by the naked eye when rubbing the manganese(ii) complexes.

Homochiral zinc(II) coordination compounds based on in-situ-generated chiral amino acid-tetrazole ligands: circular dichroism, excitation light-induced tunable photoluminescence, and energetic performance.

We employed two pairs of new in-situ-generated chiral amino acid-tetrazole ligands in constructing homochiral Zn(II) coordination compounds: [Zn(tzet)]n (1a for (S)-tzet and 1b for (R)-tzet, H2tzet = N-[2-(1H-tetrazol-5-yl)ethyl]tryptophan) and [Zn(tzep)(H2O)2]·H2O (2a for (S)-tzep and 2b for (R)-tzep, H2tzep = N-[2-(1H-tetrazol-5-yl)ethyl]proline), which were hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Structural analysis reveals that 1 features a 2D homochiral framework generated by both tetrazolate and carboxylate bridges in tzet(2-) ligands. The isolated structure of 2 is stabilized by extensive hydrogen bonds, which leads to formation of a supramolecular 2D architecture. The absolute configuration induced at the nitrogen atoms of 1 and 2 is strictly related to the neighboring chiral carbon atoms by hydrogen-bond interactions. To further investigate their chirality, the combined experimental and theoretical analyses of circular dichroism spectra reveal the absolute configurations and nature of the Cotton effects. Solid-state excitation and emission spectra for 1 and 2 at room temperature were investigated with relevant density of states calculation, and tunable photoluminescence emission of 1 under different excitation wavelengths was discussed. As nitrogen-rich tetrazolate compounds, 1 and 2 possess higher enthalpies of combustion and may serve as a new family of promising energetic materials.

4-(1H-Tetra-zol-5-yl)benzoic acid monohydrate.

The asymmetric unit of the title compound, C(8)H(6)N(4)O(2)·H(2)O, consists of one 4-(1H-tetra-zol-5-yl)benzoic acid mol-ecule and one water mol-ecule. Hydrogen-bonding and π-π stacking (centroid-centroid distance between tetra-zole and benzene rings = 3.78 Å) inter-actions link the mol-ecules into a three-dimensional network.

Unprecedented (3,10)-connected 2-D metal-organic framework constructed from octanuclear cobalt(II) clusters and a new bifunctional ligand.

A metal-organic framework with the highest connectivity of 2-D topology was first assembled from an octacobalt(II) cluster as a 10-connected node and a new bifunctional ligand 1-(3,5-dicarboxy-phenyl)-4-phenyl-1H-1,2,3-triazole as a 3-connected node as well as "double bridge" linkers.

Two Cu2 and Zn2 metallamacrocycles featuring a novel extended pi-conjugated carbazole bridge.

Two neutral dinuclear metallamacrocycles, [Cu2(hbca)2].2CHCl3.2H2O (1) and [Zn2(hbca)2].7H2O (2), have been assembled from reactions of the new rigid carbazole-based ligand H2hbca [N,N'-bis(2-hydroxobenzylidene)-9H-carbazole-3,6-diamine] with copper(II) or zinc(II) acetate. The extended aromatic ligand spacer is responsible for intermetallic antiferromagnetic exchange, which is rationalized using the spin-polarization formalism with the help of density functional theory calculations.

Copper complex of an iminodioxabicyclo[3.3.1]nonane pendant ligand: the first example of iminodioxocin bridgehead nitrogen coordination.

The pentadentate N4O amine-imine-naphthol ligand (HL(D)) containing rigid 8,16-imino-8H,16H-dinaphtho[2,1-b:2,1-f][1,5]dioxocin is formed preferentially, under visible light irradiation conditions, instead of the product H3L, expected from imidazolidine ring formation. A strained chelate bite enforces the first bridgehead nitrogen coordination to a copper(II) ion from the bicyclic iminodioxocin part of the ligand as shown by X-ray crystallography.

A new type of hybrid magnetic semiconductor based upon polymeric iodoplumbate and metal-organic complexes as templates.

A new type of one-dimensional organic-inorganic hybrid [M(en)3]Pb2I6 [M = Mn (1), Fe (2), Zn (3), Ni (4); en = ethylenediamine] has been obtained and structurally characterized by X-ray crystallography, which opens a new approach to construct hybrid magnetic semiconductors. The results of optical absorption spectra and theoretical calculations for compounds 1-3 reveal a quantum confinement effect, and the variable-temperature magnetic susceptibility measurements for 1, 2, and 4 indicate ferromagnetic, antiferromagnetic, and paramagnetic behavior, respectively.

Two halogeno(cyano)cuprates with long-lived and strong luminescence.

Solvothermal reactions of copper(I) cyanide with tetramethylammonium salts in anhydrous tetrahydrofuran (THF) lead to two novel halogeno(cyano)cuprates, namely, [Me(4)N][Cu(3)(CN)(2)Br(2)] (1) with a 1-D ribbon motif and [Me(4)N](2)[Cu(4)(CN)(5)Cl] (2) with a 3-D nanoporous framework. In 1, four Cu(I) ions are connected via two mu-Br and two mu(3)-Br atoms into a neutral [Cu(4)Br(4)] cluster, and such clusters are further double bridged by [Cu(CN)(2)](2-) linkers to form a 1-D ribbonlike chain. While in 2, Cu(I) ions are connected via mu-CN and mu(3)-CN ligands and mu-Cl atoms into a 2-D fluctuant sheet along the a-c plane, and these sheets are further linked by another kind of mu-CN ligand to form a 3-D nanoporous framework in whose channels reside [Me(4)N](+) cations. Results of optical and luminescent studies indicate that both two complexes are potential materials for semiconductors and long-lived highly luminescent materials.

Two series of novel rare earth complexes with dicyanamide [Ln(dca)2(phen)2(H2O)3][dca].(phen), (Ln = Pr, Gd, and Sm) and [Ln(dca)3(2,2'-bipy)2(H2O)]n, (Ln = Gd, Sm, and La): syntheses, crystal structures, and magnetic properties.

Two series of novel complexes, [Ln(dca)(2)(Phen)(2)(H(2)O)(3)](dca).(phen) (Ln = Pr (1), Gd (2), and Sm (3), dca = N(CN)(-), phen = 1,10-phenanthroline) and [Ln(dca)(3)(2,2'-bipy)(2)(H(2)O)](n), (Ln = Gd (4), Sm (5), and La (6), 2,2'-bipy = 2,2'-bipydine), have been synthesized and structurally characterized by X-ray crystallography. The crystal structures of the first series (1-3) are isomorphous and consist of discrete [Ln(dca)(2)(Phen)(2)(H(2)O)(3)]+ cations, dca anions, and lattice phen molecules; whereas the structures of the second series (4-6) are characterized by infinite chains [Ln(dca)(3)(2,2'-bipy)(2)(H(2)O)](n). The Ln(III) atoms in all complexes are nine-coordinated and form a distorted tricapped trigonal prism environment. The three-dimensional frameworks of 1-6 are constructed by intermolecular hydrogen bond interactions. Variable-temperature magnetic susceptibility measurements for complexes 1, 2, 4, and 5 indicate a Curie-Weiss paramagnetic behavior over 5-300 K.

Zinc complexes of T-shaped trans-1,2,3-propenetricarboxylic acid with 1-D ribbon-like chain, 2-D rhombus-grid-like and herringbone-like layers, and non-interpenetrating 3-D open framework.

Five zinc complexes of T-shaped trans-1,2,3-propenetricarboxylic acid (H(3)L) with 1-D ribbon-like chain, 2-D rhombus-grid-like and herringbone-like layers, and non-interpenetrating 3-D open framework have been obtained based on different building blocks. X-ray single crystal analyses show that the T-shaped information of H(3)L was nicely expressed in the construction of herringbone-like or ladder-like structure. All compounds were found to display blue fluorescent emissions.

A one-dimensional copper coordination polymer containing both dicyanamide and 1,10-phenanthroline ligands.

The crystal structure of catena-poly[[[acetato(1,10-phenanthroline-kappa(2)N,N')copper(II)]-micro-dicyanamido-kappa(2)N(1):N(5)] trihydrate], [[Cu(C(2)H(3)O(2))(C(2)N(3))(C(12)H(8)N(2))].3H(2)O](n), consists of a zigzag chain formed by the polymer [Cu(CH(3)COO)(dca)(phen)](n) (phen is 1,10-phenanthroline and dca is dicyanamide), with three water molecules per repeat unit of the polymer. The Cu(II) atom has a slightly distorted square-pyramidal coordination environment consisting of two N atoms of the phen ligand, two nitrile N atoms of different dca ligands, one of them axial, and one O atom of the acetate anion. The compound forms a one-dimensional chain using dca as an end-to-end bridging ligand. Non-covalent interactions, pi-pi stacking and hydrogen bonding mediate the bundling of the polymer chains into a three-dimensional structure, with the water molecules playing an important role in the hydrogen bonding.