On the topological representation of catalytic cycles with nonlinear steps

Reaction route analysis is applied to visualize reaction networks in several heterogeneous catalytic reactions. Combination of the theory of complex reactions with the notion of catalytic cycles results in a topological representation of complex mechanisms with the nodes comprising all possible surface species including free sites and branches indicating interconnections between reactions.     

Azine bridged silver coordination polymers: Powder X-ray diffraction route to crystal structure determination of silver benzotriazole

In continuation of our interest in solid-state structures of silver complexes of photographic importance, the structure for silver benzotriazole (AgBZT), has now been obtained. The preferred method for solving crystal structures is via single-crystal X-ray diffraction (XRD). However, for some materials, growing single crystals of appropriate size and quality is often difficult or even impossible. AgBZT is an example of such a silver complex with poor solubility. The usual routes to preparing single crystals using recrystallization from a cooperating solvent resulted in polycrystalline powder samples. We propose a crystal structure for AgBZT, solved from synchrotron X-ray powder diffraction data, using a direct-space Monte Carlo simulated annealing approach. AgBZT crystals are monoclinic, (P2₁/c), with unit cell dimensions, a=14.8052(3) Å, b=3.7498(4) Å, c=12.3495(12) Å, and β=114.200(6)°. The AgBZT complex is constructed from all three of the Benzotriazole (BZT) nitrogens bonding to a separate silver atom. As a consequence of this bonding mode, the structure is a highly cross-linked, coordination polymer.     

Assembly and Photophysics of Ternary Luminescent Lanthanide Molecular Complex Systems

In this paper, according to the molecular fragment principle, a series of eight ternary luminescent lanthanide complex systems were assembled, and whose compositions were determined with elemental analysis and infrared spectrum: Ln(MA)₃(L)·H₂O, where Ln = Sm, Eu, Tb, Dy; HMA = α‐methylacrylic acid; L = 1,10‐phenanthroline (phen), 2,2′‐bipyridine (bipy). The photophysical properties of these functional molecular systems were studied with ultraviolet‐visible absorption spectrum, and fluorescence excitation and emission spectrum. It was found that the heterocylic compounds (phen and bipy) act as the main energy donor and luminescence sensitizer for their suitable energy match and effective energy transfer to the emission energy level of Ln³⁺ ions. MMA ligand was only used as the terminal structural ligand to influence the luminescence. Especially terbium complex systems show the strongest luminescence for the optimum energy match and transfer between phen (bipy) and Tb³⁺ ion.     

Mechanism of Interaction of γ-Halogenated Salts of Pyrylium and Benzopyrylium with Aromatic Amines

Stoichiometry and kinetics of reactions of 2,6-diphenyl-4-chloropyrylium, 4-chloroflavylium, 4-bromoflavylium, and 4-iodoflavylium perchlorates with nucleophiles N,N-dimethylaniline and n-phenylenediamine are studied using cyclic voltammetry and spectroscopy. Nucleophilic substitution in these compounds proceeds via the formation of a charge-transfer complex, which converts into a radical ion pair as a result of the electron transfer. Heterolytic clevage of the C–Hal bond occurs at the stage of pyranyl (flavanyl) radical.     

Dimer of Bis[trans-5-methyl-2-[2-（4-methoxylphenyl） ethenyl]-benzoxazole]di-μ-nitratosilver（I）

1 INTRODUCTION We are presently involved in the synthesis and photodimerization of the analogues of trans-2-sty- rylbenzoxazole (BOEP), which have been widely reported as fluorescent whiteners and remedies[1]. Some structures of BOEP derivatives and thei…     

Geometry and electronic structure of a heterometallic cluster Mo<Subscript>2</Subscript>Mg<Subscript>2</Subscript> in different oxidation states of Mo: a DFT study

Reduction of tetranuclear heterometallic complex Mo₂Mg₂ was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex [Mo^VIO₂Mg(MeOH)₂(OMe)₄]₂ and a partially reduced Mo^V complex are in good agreement with experimental data. The reduced Mo^III complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with release of a coordination position at the Mo atoms requires small energy expenditure. One can assume that the reduction of the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–457, March, 2008.     

Synthesis,X-Ray Structure and Characterization of a Triruthenium Cluster Complex Ru_3~Ⅲ(μ_3-O)(μ-CH_3COO)_6(py)_2Cl with Four Steps One-electron Redox Processes

Great attention is currently paid to the synthesis of polynuclear transition metal complexes as well as their photochemical, photophysical, and electrochemical properties. The design of multicomponent systems capable of performing useful light- and/or redox-induced function is of special interest1. The oxo-centered carboxylate-bridge trinuclear ruthenium clusters have been investigated extensively during recent decades because they have remarkable electron-transfer properties, intense visibl…