.АРХИВ СТАТЕЙ

The title compound C24H22ClNO2 belongs to the orthorhombic system, space group Pca21 with a = 12.1771(10) ?, b = 4.9305(4) ?, c = 34.419(3) ?, a = b = g = 90°, V = 2066.5(3) ?3, Z = 4, Dc = 1.260 g/cm3, F(000) = 824, R = 0.0402 and wR = 0.1144, S = 1.034, T = 293 K. The compound is a chalcone with 4-chlorophenyl and [(5-ethyl-pyridin-2-yl)-ethoxy]-phenyl substituents bonded at the opposite ends of a propenone group, the biologically active region. The propenone bridge makes dihedral angles of 10.61(23)° and 62.75(22)° respectively, with 4-chlorophenyl and the [(5-ethyl-pyridin-2-yl)-ethoxy]-phenyl group.

Two new isostructural methoxide-bridged dimeric oxovanadium(V) complexes [VO(L1)(OMe)]2 (1) and [VO(L2)(OMe)]2 (2), where L1 and L2 are the deprotonated forms of 3-bromo-N?-[1-(2-hydroxyphenyl)ethylidene]benzohydrazide (H2L1) and 3-chloro-N?-[1-(2-hydroxyphenyl)ethy­lidene]benzohydrazide (H2L2) respectively, are synthesized and characterized by elemental analyses, IR spectra, and single crystal X-ray determination. Both crystals crystallize in the triclinic space group P-1. For 1, a = 7.5237(15) ?, b = 10.846(3) ?, c = 11.195(3) ?, a = 84.143(3)°, b = 72.244(3)°, g = 77.869(3)°, V = 849.9(4) ?3, Z = 1, R1 = 0.0634, wR2 = 0.1373. For 2, a = 7.493(2) ?, b = 10.740(3) ?, c = 11.109(3) ?, a = 84.569(2)°, b = 71.783(2)°, g = 79.822(2)°, V = 835.0(4) ?3, Z = 1, R1 = 0.0511, wR2 = 0.1076. Each V atom in the complexes is octahedrally coordinated.

A new cadmium(II) complex with (1?H-[2,2?]Biimidazoly-1-yl)-acetic acid (HBDAC) [Cd(BDAC)2(H2O)2]?H2O is synthesized and structurally characterized, which crystallizes in the monoclinic system, space group P21/c, a = 8.465(3) ?, b = 14.164(5) ?, c = 11.294(3) ?, a = 90°, b = 127.405(17)°, g = 90°, Z = 2. The [Cd(BDAC)2(H2O)2]?H2O units are further bridged by O—H…O, N—H…O, C—H…O hydrogen bonds, p—p stacking and C—O…p interactions, generating a three-dimensional supramolecular structure. In addition, luminescence measurements reveal that complex 1 exhibits strong fluorescent emission in the solid state at room temperature.

Reaction of cobalt hydroxide with the a,w-dicarboxylic acid and 1,12-dodecanedioic acid under ambient conditions results in the formation of a trihydrate Co(C12H20O4)(H2O)3 (1). Single crystal X-ray diffraction studies show 1 to crystallise in the orthorhombic space group Pccn with cell parameters a = 40.2343(7) ?, b = 8.1519(1) ?, c = 9.1011(2) ?. The structure has a very pronounced two dimensional character, with a separation of hydrophobic n-alkyl chains from the carboxylate groups, the Co2+ cations and the water of crystallisation. The structure is discussed in respect of the structures of other known compositionally related compounds, including the dihydrate Co(C12H20O4)(H2O)2.

The salt (h5-pentamethylcyclopentadienyl){bis(pentafluorophenyl)thiomethylphenylphosphine-k2S,P)chloroiridium(III) tetrafluoroborate, [(h5-C5Me5)IrCl{k2S,P-(C6F5)2PC6H4SMe-2}]BF4, crystallizes as a conglomerate in the orthorhombic crystal system in space group P212121 with unit cell parameters a = 9.9621(9) ?, b = 16.7793(15) ?, c = 18.5040(16) ?, V = 3093.1(5) ?3, Z = 4, dcalc = 2.014 g?cm–3. The structure of the SIr, SS stereoisomer reveals three-legged piano stool geometry about Ir, with Cp*—Ir, Ir—P, Ir—S and Ir—Cl distances of 1.847(5), 2.2791(14), 2.3451(13) and 2.3840(12) ? respectively.

Two zinc(II) complexes [Zn(6,6?-dimethyl-2,2?-bipy)Cl2]n (1) and [Zn(6,6?-dimethyl-2,2?-bipy)I2]n (2) are synthesized from the reaction of the 6,6?-dimethyl-2,2?-bipy ligand with ZnCl2 and ZnI2. Zinc(II) oxide nanoparticles are synthesized by the thermolysis of [Zn(6,6?-dimethyl-2,2?-bipy)Cl2]n (1) and [Zn(6,6?-dimethyl-2,2?-bipy)I2]n (2) at two different temperatures. The ZnO nanoparticles are characterized by X-ray diffraction and scanning electron microscopy (SEM). SEM images show the average size of the ZnO nanoparticles produced of 50 nm and 60 nm in compounds 1 and 2 respectively.

In the present research, we have mainly concentrated on the survey of interactions in Ln3+ (Ln = La, Ce, Nd and Sm) ternary complexes of 5,7-dichloroquinoline-8-ol (DCQ) and 4-vinyl pyridine (VP), [Ln(VP)2(DCQ)3]3+ by means of density functional theory, Hartree-Fock and Sparkle/PM3 semi-empirical computational methods. For VP and DCQ ligands, the cation bin­ding energy sequence follows the order La3+ > Ce3+ > Nd3+ > Sm3+ as expected based on increasing in the hardness and decreasing in the ionic radius of this lanthanide cation series. A similar trend was observed in the calculated binding energy of the aforesaid ligands with the hydrated lanthanide cation series [Ln(H2O)9]3+, while the computed values of deformation energy of ligands upon complexation demonstrated an opposite order in the lanthanide cation series. Moreover, the solvent effects are considered via a polarized continuum model and provided a significant increase in the binding strength while the relative magnitude of binding energies is the same as that in the gas phase. Combining quantum and statistical mechanical calculations, we have also determined quantitatively a reliable estimate of the conformational distribution of the [Sm(VP)2(DCQ)3]3+ complex at various temperatures in the gas phase by computing the molecular partition functions and consequently the analysis of the conformational equilibrium constants.

Reaction of cobalt hydroxide with the a,?-dicarboxylic acid and 1,12-dodecanedioic acid under ambient conditions results in the formation of a trihydrate Co(C12H20O4)(H2O)3 (1). Single crystal X-ray diffraction studies show 1 to crystallise in the orthorhombic space group Pccn with cell parameters a = 40.2343(7) ?, b = 8.1519(1) ?, c = 9.1011(2) ?. The structure has a very pronounced two dimensional character, with a separation of hydrophobic n-alkyl chains from the carboxylate groups, the Co2+ cations and the water of crystallisation. The structure is discussed in respect of the structures of other known compositionally related compounds, including the dihydrate Co(C12H20O4)(H2O)2.

The salt (?5-pentamethylcyclopentadienyl){bis(pentafluorophenyl)thiomethylphenylphosphine-k2S,P)chloroiridium(III) tetrafluoroborate, [(?5-C5Me5)IrC{ k2S,P-(C6F5)2PC6H4SMe-2}]BF4 ,crystallizes as a conglomerate in the orthorhombic crystal system in space group P212121 with unit cell parameters a = 9.9621(9)?,b= 16.7793(15) ?, c = 18.5040(16) ?, V= 3093.1(5) ?3, Z = 4, dcalc = 2.014 g • cm–3. The structure of the SIr, SS stereoisomer reveals three-legged piano stool geometry about Ir, with Cp*—Ir, Ir—P, Ir—S and Ir—Cl distances of 1.847(5), 2.2791(14), 2.3451(13) and 2.3840(12) ? respectively.

Two zinc(II) complexes [Zn(6,6'-dimethyl-2,2'-bipy)Cl2]n (1) and [Zn(6,6'-dimethyl-2,2'-bipy)I2]n (2) are synthesized from the reaction of the 6,6'-dimethyl-2,2'-bipy ligand with ZnCl2 and ZnI2. Zinc(II) oxide nanoparticles are synthesized by the thermolysis of [Zn(6,6'-dimethyl-2,2'-bipy)Cl2]n (1) and [Zn(6,6'-dimethyl-2,2'-bipy)I2]n (2) at two different temperatures. The ZnO nanoparticles are characterized by X-ray diffraction and scanning electron microscopy (SEM). SEM images show the average size of the ZnO nanoparticles produced of 50 nm and 60 nm in compounds 1 and 2 respectively.

In the present research, we have mainly concentrated on the survey of interactions in Ln3+ (Ln = La, Ce, Nd and Sm) ternary complexes of 5,7-dichloroquinoline-8-ol (DCQ) and 4-vinyl pyridine (VP), [Ln(VP)2(DCQ)3]3+ by means of density functional theory, Hartree-Fock and Sparkle/PM3 semi-empirical computational methods. For VP and DCQ ligands, the cation bin­ding energy sequence follows the order La3+ > Ce3+ > Nd3+ > Sm3+ as expected based on in­creasing in the hardness and decreasing in the ionic radius of this lanthanide cation series. A similar trend was observed in the calculated binding energy of the aforesaid ligands with the hydrated lanthanide cation series [Ln(H2O)9]3+, while the computed values of deformation energy of ligands upon complexation demonstrated an opposite order in the lanthanide cation series. Moreover, the solvent effects are considered via a polarized continuum model and pro­vided a significant increase in the binding strength while the relative magnitude of binding en­ergies is the same as that in the gas phase. Combining quantum and statistical mechanical cal­culations, we have also determined quantitatively a reliable estimate of the conformational dis­tribution of the [Sm(VP)2(DCQ)3]3+ complex at various temperatures in the gas phase by com­puting the molecular partition functions and consequently the analysis of the conformational equilibrium constants.