Сибирское отделение РАН (СО РАН) (Статьи)

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.