An Indium Synthetic Etioporphyrin for Organic Electronics: Aggregation and Photoconductivity in Thin Films.

A new complex of indium(III)chloride with etioporphyrin-I was synthesized and characterized. As with naturally occurring extraligated etioporphyrins, the InCl-EtioP-I spectrum in solution has a very strong B-band and a more than an order of magnitude weaker Q-band, but this difference diminishes in solid films of InCl-EtioP-I obtained by thermal evaporation in vacuum. In a solid, molecules have a tight convex-convex arrangement in a 2D double layered structure with interplane distance of 3.066 Å. The conductivity of films can easily be activated by the action of temperature or light. In the cells with symmetrical lateral contacts the photocurrent exceeds the dark current by about three orders of magnitude, with the contribution of photons in the Q-band range being greater than expected from the experimental or calculated absorption spectrum. The Q-bands contribute significantly to the photovoltaic effect in the ITO/InCl-EtioP-I/Al sandwich cells. Such cells show an untypically strong signal in the photodiode regime, which yields the spectral detectivity of 10^12 Jones.

Deprotonation of Benzoxazolium Salt: Trapping of a Radical-Cation Intermediate.

The deprotonation of N-2,6-diisopropylphenyl-substituted benzoxazolium tetrafluoroborate 1 with NaH results in the formation of electron-rich diaminodioxaethylene 2. The radical cation salt 2·+·BF4- is found to be an intermediate product in the redox reaction leading from 1 to 2.

Hydrogen-bond-assisted organocatalytic acetalization of secondary alcohols: experimental and theoretical studies.

An efficient method was developed for the acetalization of secondary alcohols in the presence of simple protic pyridinium salts. Direct correlations between the structure and activity of the synthesized catalysts were described. Stabilization via hydrogen bonding of the hemiacetal intermediate by the pyridine derivatives, along with an appropriate increase in the reaction rate, was revealed. The nature of the observed experimental acceleration of the examined reactions catalyzed by pyridinium salts comprising electron-withdrawing groups at certain positions of the pyridinium ring was studied. In this vein, the interpretation of the hydrogen-bonded pretransition-state complexes and transition-state complexes with strong catalysts was also discussed in terms of partial proton transfer. It was concluded that optimized pretransition-state complexes of the catalyst and reactant are useful for the prediction of catalyst efficiency prior to the experiment.

Bis(but-2-enoato-κO)tri-phenyl-bis-muth(V).

In the title mol-ecule, [Bi(C6H5)3(C4H5O2)2], the Bi(V) atom is in a distorted trigonal-bipyramidal environment with carboxyl-ate O atoms in axial positions and phenyl C atoms in the equatorial plane. The Bi-O bond lengths are 2.283 (3) and 2.309 (2) Å, but as a result of additional long Bi⋯O inter-actions [2.787 (3) and 2.734 (3) Å], one of the C-Bi-C angles is 148.62 (13)°. In the crystal, weak C-H⋯O hydrogen bonds connect pairs of mol-ecules into inversion dimers. These dimers are further connected by weak C-H⋯π inter-actions into chains along [100] .

Bis[(E)-3-(4-meth-oxy-phen-yl)prop-2-enoato]triphenyl-anti-mony(V) benzene monosolvate.

The asymmetric unit of the title compound, [Sb(C6H5)3(C10H9O3)2]·C6H6, contains one organometallic mol-ecule and one benzene mol-ecule that is disordered over two sets of sites with an occupancy ratio of 0.556 (15):0.444 (15). The Sb(V) atom is in a distorted trigonal-bipyramidal environment with the carboxyl-ate O atoms in axial positions and phenyl C atoms in the equatorial plane. As a result of additional Sb⋯O inter-actions, one of the C-Sb-C angles is widened to 140.19 (6)°.

Polytypism and oxo-tungstate polyhedra polymerization in novel complex uranyl tungstates.

Three new uranyl tungstates, α-, ß-Cs(2)[(UO(2))(2)(W(2)O(9))], and Rb(6)[(UO(2))(7)(WO(5))(2)(W(3)O(13))O(2)], have been obtained by high temperature solid state reactions. All three compounds display novel structure topologies: α- and ß-Cs(2)[(UO(2))(2)(W(2)O(9))] are based upon layers with a new topology that can be related to the uranophane topology; Rb(6)[(UO(2))(7)(WO(5))(2)(W(3)O(13))O(2)] is a rare example of a non-molecular inorganic phase with layers containing oxo-tungstate trimers. The structural relationship between α- and ß-Cs(2)[(UO(2))(2)(W(2)O(9))] can be assigned to polytypism.