Synthesis, structure, spectroscopic properties, and photochemistry of homo- and heteropolynuclear copper(I) complexes bridged by the 2,5-bis(2-pyridyl)pyrazine ligand

Cu(I)-Cu(I) and Cu(I)-Ru(II) dinuclear complexes bridged by the 2,5-bppz (2,5-bis(2-pyridyl)pyrazine) ligand have been prepared and characterized including the X-ray crystallographic study of the dinuclear [{CuI(PPh3)2}2(mu-2,5-bppz)](PF6)2)2CH3Cl complex: a = 13.974(2), b = 13.993(2), c = 13.537(2) A; alpha = 101.98(1), beta = 103.22(1), gamma = 113.90(1) degrees ; triclinic, P, Z = 1. The trinuclear [{(bpy)2RuII(mu-2,5-bppz)}2CuI](PF6)5 complex was also prepared, and the structure of the complex in solution was studied by spectrometric titration. The dinuclear Cu(I) complex and [(bpy)2RuII(mu-2,5-bppz)CuI(PPh3)2](PF6)5 show photoluminescence in the solid state, which should arise from MLCT states. Photochemical oxidation of the trinuclear RuII2CuI complex occurs in the presence of oxygen to give a RuII2CuII complex. The MLCT states and the redox reaction in the excited state are discussed.     

Correlation between dynamic heterogeneity and medium-range order in two-dimensional glass-forming liquids

A glassy state of matter results if crystallization is avoided upon cooling or increasing density. However, the physical factors controlling the ease of vitrification and nature of the glass transition remain elusive. Using numerical simulations of polydisperse hard disks, we find a direct relation between medium-range crystalline ordering and the slow dynamics which characterizes the glass transition. This suggests an intriguing scenario that the strength of frustration controls both the ease of vitrification and nature of the glass transition. Vitrification may be a process of hidden crystalline ordering under frustration, at least in our system.     

Direct observation of the unstable intermediates in radical addition reaction by using an interfacing microchip combined with an NMR

Direct observation of the unstable intermediate in the radical addition reaction of the oxime ether 1 mediated by triethylborane (Et(3)B) is described using (1)H and (11)B micro channeled cell for synthesis monitoring (MICCS), which was recently developed as an interfacing microchip for NMR. It was possible that the signal of the intermediate was observed as a result of using MICCS technique with a standard NMR instrument. This result supports the structure of the intermediate analyzed by diffusion-ordered spectroscopy (DOSY) NMR method in a previous paper. The procedure of micro channeled cell for synthesis monitoring-nuclear magnetic resonance (MICCS-NMR) was much easier than that of DOSY method. It was proven that it could be applied to the reaction in an anhydrous condition.     

Morphology of F8T2/PC71BM Blend Film as Investigated by Scanning Transmission X-ray Microscope (STXM)

Clarification of the morphology of bulk heterojunction (BHJ) is indispensable for true comprehension of the organic solar cells. Here, we performed scanning transmission X-ray microscopy (STXM) for a poly-(9,9-dioctylfluorene-co-bithiophene) (F8T2)/[6,6]-phenyl C71-butyric acid methyl ester (PC₇₁BM) blend film annealed at various temperatures (T_an). We found that the fullerene concentration within the polymer-rich domain decreases with T_an while the domain size (～230 nm) is essentially unchanged. We will discuss the interrelation between the film morphology and the photovoltaic performance.     

Ligand dependence of pi-complex character in disilene-palladium complexes

The synthesis and structures of new 16-electron disilene palladium complexes with 2,6-dimethylphenyl isocyanide and phenyldimethylphosphine ligands [L(1)L(2)Pd{(t-BuMe(2)Si)(2)Si=Si(SiMe(2)Bu-t)(2)}, where L(1) = L(2) = PhMe(2)P; L(1) = (cyclohexyl)(3)P, L(2) = 2,6-dimethylphenyl isocyanide; L(1) = L(2) = 2,6-dimethylphenyl isocyanide] are described. Comparison of the X-ray structural parameters around the disilene moiety among these complexes and related bis(trimethylphosphine)(disilene)palladium and 14-electron (tricyclohexylphosphine)(disilene)palladium revealed that the pi-complex character is sensitive to the residual ligands and increases with decreasing the strength of sigma-donation from the ligands.     

Synthesis, properties, and reactions of a series of stable dialkyl-substituted silicon-chalcogen doubly bonded compounds

The first dialkyl-substituted silicon-chalcogen doubly bonded compounds [R2Si=X; R2=1,1,4,4-tetrakis(trimethylsilyl)butane-1,4-diyl, X = S (4), Se (5), and Te (6)]were synthesized by the reactions of an isolable dialkylsilylene R2Si: (3) with phosphine sulfide, elemental selenium, and elemental tellurium, respectively. Systematic changes of characteristics of silicon-chalcogen double bonds are elucidated by X-ray analysis, UV-vis spectroscopy, and DFT calculations. In the solid state, the unsaturated silicon atom in 4-6 adopts planar geometry and the extent of the shortening of Si=X double bonds from the corresponding Si-X single bonds decreases in the order 4 > 5 > 6. In the absorption spectra of 4-6, pi -->pi* transition bands are observed distinctly in addition to n -->pi* transition bands. Both the n -->pi* and pi -->pi* transitions are red-shifted in the order 4 < 5 < 6, and the difference between the energies of the two transitions is kept almost constant among 4-6. The tendency is explained using the qualitative perturbation theory and is reproduced by the DFT calculations for model silanechalcogenones. Addition reactions of water, methanol, and isoprene to 4-6 are reported.     

On a new construction of geometric mean of -operators

For n positive definite operators A₁,…,A_n, Ando-Li-Mathias defined geometric mean of n-operators by symmetric procedure. It has many nice properties, and is studied by many authors. But the process is so complicated to compute. In this paper, we shall attempt to make a new construction of geometric mean of n-operators which we can compute it easier than geometric mean by Ando–Li–Mathias.