Incorporation of phenanthrene into a hexaphyrin(1.1.1.1.1.0) frame resulted in intramolecular ring fusion, thus giving rise to chiral helicenophyrins. These molecules contain helicene and porphyrin features by incorporating either an aza[5]helicene or heptacyclic S-shaped aza[5]helicene.

Absorption emission and excitation spectra are measured and analyzed to achieve assignments of energy levels for 4f(N) ions in Ba(2)YCl(7):RE(3+) (RE = Pr, Nd, Tb, Dy, Ho, Er, and Tm) crystals. The experimental energy levels were analyzed in terms of the usual free-ion parameters and the crystal field (CF) ones, B(kq), in the Wybourne notation. The orthorhombic C(2v) symmetry is shown to be a good approximation of the actual triclinic C(1) site symmetry at the metal center. The starting values of the CF parameters B(kq) used for fittings for the studied crystals were obtained from superposition model analysis. A good agreement between the calculated and experimental energy levels was obtained with rms deviations in the range from 6.8 cm(-1) (for Ho(3+)) to 14.1 cm(-1) (for Pr(3+)). The fitted sets of B(kq) parameters are, in general, consistent across the 4f(N) series. This study has enabled determination and discussion of the trends in variation of the free-ion parameters and CF ones across the 4f(N) series. The CF parameter set and energy level structure obtained for Nd(3+) ion in Ba(2)YCl(7) crystal are consistent with those for Nd(3+) in structurally related RbY(2)Cl(7) crystal. This systematic analysis of CF parameters is one of only few such studies encompassing nearly whole series of RE(3+) ions.

Novel room-temperature ferroelectric crystals with complex sequences of phase transitions.

The reactions of a series of 1-halopolyynes with secondary amines led to novel amine end-capped polyynes exhibiting surprisingly high stability toward moisture. The new compounds were characterized by NMR spectroscopy, ESI-MS spectrometry, and X-ray single-crystal diffractometry. The use of amine end-capped polyynes as precursors to substituted push-pull thiophenes was next presented. The results show the first-to the best of our knowledge-transformation of ynamine to thiophene and the first regioselective transformation of a longer polyynes to butadiyne-substituted thiophene. Photophysical studies of the resulting compounds show that some of the substituted thiophenes have high quantum yield photoluminescence upon UV light irradiation.