Structural characteristics and non-linear optical behaviour of a 2-hydroxynicotinate-containing zinc-based metal-organic framework.

Materials with non-linear optical (NLO) properties play an important role in the construction of electronic devices for optical communications, optical data processing and data storage. With this aim in mind, a Zn(II)-based metal-organic framework {[Zn2(nica)2(bpy)1.5(H2O)]×0.5(bpy)×3H2O}n (1), was synthesized using 4,4'-bipyridine (bpy) and a potentially bidentate ligand, 2-hydroxynicotinic acid (H2nica) with a salicylate binding moiety. A single-crystal X-ray diffraction analysis revealed that compound 1 crystallized in the orthorhombic space group Fdd2 and was composed of a three dimensional porous framework. Since Fdd2 belonged to a class of non-centrosymmetric space groups, we therefore investigated the non-linear optical behaviour of compound 1. Photoluminescence studies revealed that compound 1 exhibited a blue light emission with a maxima at 457 nm.

Anthracene/phenothiazine π-conjugated sensitizers for dye-sensitized solar cells using redox mediator in organic and water-based solvents.

Metal-free dyes (MD1 to MD5) containing an anthracene/phenothiazine unit in the spacer have been synthesized. The conversion efficiency (7.13 %) of the dye-sensitized solar cell using MD3 as the sensitizer reached approximately 85 % of the N719-based standard cell (8.47 %). The cell efficiency (8.42 %) of MD3-based dye-sensitized solar cells (DSSCs) with addition of chenodeoxycholic acid is comparable with that of N719-based standard cell. The MD3 water-based DSSCs using a dual-TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl)/iodide electrolyte exhibited very promising cell performance of 4.96 % with an excellent Voc of 0.77 V.

Structures, molecular orbitals and UV-vis spectra investigations on Br2C6H4: a computational study.

The dibromobenzenes (1,2-, 1,3- and 1,4-Br2C6H4) have been studied by theoretical methods. The structures of these species are optimized and the structural characteristics are determined by density functional theory (DFT) and the second order Møller-Plesset perturbation theory (MP2) levels. The geometrical structures of Br2C6H4 show a little distortion of benzene ring due to the substitution of highly electronegativity of bromine atoms. The electronegativity of bromine atoms in 1,4-Br2C6H4 is predicted to be more negative than 1,2- and 1,3-Br2C6H4. In addition, dipole moment and frontier molecular orbitals (FMOs) of these Br2C6H4 are performed as well. The 1,4-Br2C6H4 is slightly more reactive than 1,2- and 1,3-Br2C6H4 because of its small HOMO-LUMO energy gap. The simulated UV-vis spectra are investigated by time-dependent density functional theory (TD-DFT) approach, which are in excellent agreement with the available experimental value. Our calculations show that a few of absorption features are between 140nm and 250nm, which is in ultraviolet C range, and the red shift of 1,3- and 1,4-Br2C6H4 are predicted. Moreover, the UV absorption features of these Br2C6H4 in water or methanol are predicted to be more intense than in gas phase due to solvent effect.

[Hydridotris(pyrazol-1-yl-κN(2))borato]bis-(methyl-amino-κN)(triphenyl-phos-phine-κP)ruthenium(II) chloride dichloro-methane solvate monohydrate.

The title salt, [Ru(Tp)(CH(5)N)(2)(PPh(3))]Cl·CH(2)Cl(2)·H(2)O [where Tp is (C(3)H(3)N(2))(3)BH and PPH(3) is C(18)H(15)P], has the Ru(III) atom in an octa-hedral geometry; one of the Ru-N(Tp) bonds [2.135 (8) Å] is slightly longer than another two, owing to the trans influence of PPh(3) ligand. N-H⋯Cl and O-H⋯Cl hydrogen bonding leads to the formation of layers parallel to (100).

(Ammine)(carbon-yl)[hydridotris(pyrazol-1-yl-κN(2))borato](triphenyl-phosphine-κP)ruthenium(II) chloride dichloro-methane disolvate.

In the title compound, [Ru(CO)(NH(3))(C(9)H(10)BN(6))(C(18)H(15)P)]Cl·2CH(2)Cl(2), the coordination environment around the Ru(II) atom is distorted octa-hedral. One of the Ru-N(Tp) [Tp = hydridotris(pyrazol-1-yl)borate] bond lengths is slightly longer than the other two as a result of the influence of the trans CO ligand. In the crystal, N-H⋯Cl hydrogen bonds link the complex cations and Cl(-) anions. π-π inter-actions between the pyrazole rings [centroid-centroid distance = 3.764 (3) Å] are also present.

Ruthenium-catalyzed oxidation of a carbon-carbon triple bond: facile syntheses of alkenyl 1,2-diketones from alkynes.

A new oxidation procedure of alkynes catalyzed by Tp(PPh(3))(CH(3)CN)Ru-Cl is presented, which provides an efficient way to obtain alkenyl 1,2-diketones via ruthenium alkenyl 1,2-diketone intermediates. In contrast, the analogous reactions with Tp(PPh(3))(PhCN)Ru-Cl gave rise to the ruthenium metallacycle complexes.

Proton-induced reactivities of ruthenium azido complexes: the first example of boron-carbon bond formation by methylene insertion into a B-H bond.

Whereas the reaction of Tp(PhCN)(PPh(3))Ru-N(3) {Tp = HB(pz)(3), pz = pyrazolyl} with CH(3)I in CH(2)Cl(2) led to the cationic ruthenium methyleneimine complex [Tp(PPh(3))(PhCN)Ru(NH=CH(2))]I, the analogous reaction with HCl gave rise to the ruthenium chloride complex containing a methyl tris(pyrazolyl)borate ligand (Me)Tp(PPh(3))(PhCN)RuCl, as a result of the highly unusual methylene insertion into a B-H bond of the Tp ligand.

Chlorido[hydridotris(pyrazol-1-yl-κN)borato](1H-pyrazole-κN)(triphenyl-phosphine-κP)ruthenium(II).

In the title compound, [Ru(C(9)H(10)BN(6))Cl(C(3)H(4)N(2))(C(18)H(15)P)], the Ru(II) atom is coordinated by an N,N',N''-tridentate hydrido-trispyrazolylborate (Tp) ligand, a pyrazole (HPz) mol-ecule, a chloride ion and a triphenyl-phosphine ligand, resulting in a distorted RuClPN(4) octa-hedral coordination for the metal ion: the tridentate N atoms occupy one octa-hedral face and the Cl and P atoms are cis. One of the phenyl rings is disordered over two orientations in a 0.547 (10):0.453 (10) ratio, and a weak intra-molecular N-H⋯Cl hydrogen bond generates an S(5) ring.

Azido-(benzonitrile-κN)[hydrido-tris(pyrazol-1-yl-κN)borato](triphenyl-phosphine-κP)ruthenium(II).

Facile ligand substitution is observed when the ruthenium-azide complex, [RuN(3)(Tp)(PPh(3))(2)] [Tp,HB(pz)(3), pz = pyrazol-yl, PPh(3) = triphenyl-phosphine] is treated with benzo-nitrile, yielding the title compound, [Ru(C(9)H(10)BN(6))(N(3))(C(7)H(5)N)(C(18)H(15)P)]. The asymmetric unit contains two crystallographically independent mol-ecules. In each one, the Ru(II) atom is six-coordinated in a distorted octa-hedral geometry by five N atoms from an htpb ligand, an azide ligand and a benzonitrile ligand and one P atom from a triphenyl-phosphine (tpp) ligand. The azide group is almost linear and is coordinated to Ru with an average Ru-N-N angle of 124.9 (3)°.

Methyl 1-benzyl-1H-1,2,3-triazole-4-carboxyl-ate.

In the title compound, C(11)H(11)N(3)O(2), prepared by the [3+2] cycloaddition reaction of benzyl azide with methyl propiolate, the dihedral angle between the ring planes is 67.87 (11)°.

Reactions of Tp(NH[double bond, length as m-dash]CPh(2))(PPh(3))Ru-Cl with HC[triple bond, length as m-dash]CPh in the presence of H(2)O: insertion/hydration products.

The reaction of benzophenone imine complex (NH[double bond, length as m-dash]CPh(2))[Ru]Cl {[Ru] = Tp(PPh(3))Ru; Tp = HB(pz)(3), pz = pyrazolyl} with HC[triple bond, length as m-dash]CPh in the presence of H(2)O afforded the cis-alkynyl(vinylidene) complex [Ru](C[triple bond, length as m-dash]CPh)([double bond, length as m-dash]C[double bond, length as m-dash]CHPh) , as well as two alkenyl ketone regioisomers [Ru]C(CH(2)Ph)[double bond, length as m-dash]CHC(O)Ph and [Ru]C(Ph)[double bond, length as m-dash]CHC(O)CH(2)Ph . The combination of insertion and hydration process resulted in the unprecedented formation of the alkenyl ketone complexes.

(Benzonitrile-κN)chlorido[hydrido-tris(pyrazol-1-yl-κN)borato](triphenyl-phosphine-κP)ruthenium(II) ethanol solvate.

The reaction of [Ru(C(9)H(10)BN(6))Cl(C(18)H(15)P)(2)] with benzo-nitrile leads to crystals of the title compound, [Ru(C(9)H(10)BN(6))Cl(C(18)H(15)P)(C(7)H(5)N)]·C(2)H(5)OH. In the crystal structure, the environment about the ruthenium metal center corresponds to a slightly distorted octa-hedron with an average N-Ru-N bite angle of the Tp ligand of 86.6 (2)°.

Erratum: (Benzonitrile-κN)chlorido[hydrido-tris(pyrazol-1-yl-κN)borato](triphenyl-phosphine-κP)ruthenium(II) ethanol solvate. Corrigendum.

The author list in the paper by Tong, Hung, Wang, Lin & Lo [Acta Cryst. (2009), E65, m438] is corrected.[This corrects the article DOI: 10.1107/S1600536809010265.].

(O,O'-Diethyl dithio-phosphato-κS,S')(hydridotripyrazol-1-ylborato-κN,N,N)(triphenyl-phosphine-κP)ruthenium(II).

Reaction of [Ru(Tp)Cl(PPh(3))(2)] {where Tp is hydridotri-pyrazol-yl-borate, BH[C(3)H(3)N(2))(3))]} with NH(4)[S(2)P(OEt)(2)] in methanol afforded the title compound, [Ru(C(9)H(10)BN(6))(C(4)H(10)O(2)PS(2))(C(18)H(15)P)], in which the Ru(II) ion is in a slightly disorted octa-hedral coordination environment. The [S(2)P(OEt)(2)](-) ligand coordinates in a chelating mode with two similar Ru-S bond lengths and a slightly acute S-Ru-S angle. The atoms of both -OCH(2)CH(3) groups of the diethyl dithio-phosphate ligand are disordered over two sites with approximate occupancies of 0.76 and 0.24.

(Benzophenone imine-κN)-chlorido(hydrido-tripyrazolyl-borato)-(triphenyl-phosphine)ruthenium(II) diethyl ether solvate.

The reaction of RuCl(Tp)(Ph(3)P)(2), where Tp is [(CH)(3)N(2)](3)BH, with benzophenone imine leads to the formation of the title compound, [Ru(C(9)H(10)BN(6))Cl(C(13)H(11)N)(C(18)H(15)P)]·C(4)H(10)O. The environment about the Ru atom corresponds to a slightly distorted octa-hedron and the bite angle of the Tp ligand produces an average N-Ru-N angle of 86.3 (9)°. The three Ru-N(Tp) bond lengths [2.117 (2), 2.079 (2) and 2.084 (2) Å] are slightly longer than the average distance (2.038 Å) in other ruthenium-Tp complexes.

Azido-(1,1-diphenyl-methanimine-κN)[hydridotris(pyrazolyl-κN)borato](triphenyl-phosphine-κP)ruthenium(II) diethyl ether solvate.

The reaction of [RuCl(C(9)H(10)BN(6))(C(18)H(15)P)(2)] with benzo-phenone imine in methanol, in the presence of sodium azide, leads to the formation of the title compound, [Ru(C(9)H(10)BN(6))(N(3))(HN=CPh(2))(C(18)H(15)P)]·C(4)H(10)O, which crystallizes as the diethyl ether solvate. In the crystal structure, the Ru atom is coordinated by three N atoms of one hydridotris(pyrazoly)borate anion, one P atom of one triphenyl-phosphine ligand, one N atom of the azide anion and one N atom of the benzophenone-imine ligand in a slightly distorted octa-hedral geometry. The azide anion is almost linear [177.0 (5)°], with an Ru-N-N angle of 125.9 (3)°. There is a small difference between the N-N distances [1.200 (5) and 1.164 (5) Å], the longer bond being adjacent to the Ru atom.

(Dithio-benzoato-κS,S')[hydridotris(pyrazol-1-yl-κN)borato](triphenyl-phosphine-κP)ruthenium(II).

Reaction of [Ru(Tp)Cl(PPh(3))(2)] (Tp = hydridotrispyrazolyl-borate) with ammonium dithio-benzoate in methanol leads to the formation of the title compound, [Ru(C(9)H(10)BN(6))(C(7)H(5)S(2))(C(18)H(15)P)]. In the crystal structure, the Ru atom is coordinated by three N atoms of the Tp ligand, one P atom of the triphenyl-phosphine ligand and the two S atoms of the dithio-benzoate ligand within a slightly distorted octa-hedron. The Ru-S bonds are slightly different [2.321 (1) and 2.396 (1) Å] and the average N-Ru-N angle is 86.31°.

Methyl-ene bis-(dithio-benzoate).

In the title compound, C(15)H(12)S(4), two phenyl-dithio-carboxyl-ate units are linked through a methyl-ene C atom on a twofold rotation axis. The central S-CH(2)-S angle of 116.9 (5)° is significantly larger than the ideal tetra-hedral value. The dihedral angle formed by the two phenyl rings is 68.2 (1)°. The refined Flack parameter of 0.2 (3) does not permit unambiguous determination of the absolute structure.