Dynamics of guest molecules in PHTP inclusion compounds as probed by solid-state NMR and fluorescence spectroscopy.

Partially deuterated 1,4-distyrylbenzene () is included into the pseudohexagonal nanochannels of perhydrotriphenylene (PHTP). The overall and intramolecular mobility of is investigated over a wide temperature range by (13)C, (2)H NMR as well as fluorescence spectroscopy. Simulations of the (2)H NMR spectral shapes reveal an overall wobble motion of in the channels with an amplitude of about 4 degrees at T = 220 K and 10 degrees at T = 410 K. Above T = 320 K the wobble motion is superimposed by localized 180 degrees flips of the terminal phenyl rings with a frequency of 10(6) Hz at T = 340 K. The activation energies of both types of motions are around 40 kJ mol(-1) which imply a strong sterical hindrance by the surrounding PHTP channels. The experimental vibrational structure of the fluorescence excitation spectra of is analyzed in terms of small amplitude ring torsional motions, which provide information about the spatial constraints on by the surrounding PHTP host matrix. Combining the results from NMR and fluorescence spectroscopy as well as of time-dependent density functional calculations yields the complete potential surfaces of the phenyl ring torsions. These results, which suggest that intramolecular mobility of is only reduced but not completely suppressed by the matrix, are corroborated by MD simulations. Unrealistically high potential barriers for phenyl ring flips are obtained from MD simulations using rigid PHTP matrices which demonstrate the importance of large amplitude motions of the PHTP host lattice for the mobility of the guest molecules.

Tetra-t-butyl magnesium phthalocyanine on gold: electronic structure and molecular orientation.

In this work we have investigated the electronic structure and the molecular orientation of (t-Bu)(4)PcMg (tetra-t-butyl magnesium phthalocyanine) on polycrystalline and single crystalline gold substrates using photoemission spectroscopy and x-ray absorption spectroscopy, and we compare the results to the unsubstituted PcCu (copper phthalocyanine). The C 1s photoemission spectrum is described similar to unsubstituted relatives with an additional component for the aliphatic substituents. The variation of the excitation energy causes distinct differences in the shape of the C 1s spectrum, which is very useful for the analysis of the molecular orientation in the uppermost layer. It is shown that despite of the sterically demanding substituents, ordered sublimed films of (t-Bu)(4)PcMg are accessible, the orientation of the molecules, however, is different from the orientation of the unsubstituted relatives.

Synthesis and separation of structural isomers of 2(3),9(10),16(17),23(24)-tetrasubstituted phthalocyanines.

The 2(3),9(10),16(17),23(24)-tetrasubstituted metalphthalocyanines 1-7 (M = In, Ni, Zn) were synthesized, as mixtures of four different structural isomers, from the corresponding 4-alkoxy-1,2-dicyanobenzenes and the appropriate metal salts. Separation of the four structural isomers was successfully achieved on a C30 alkyl phase by high-performance liquid chromatography (HPLC). The determination of the point groups of the structural isomers was carried out for 1 and 3, the composition of the structural isomers of 4-7 was accomplished by comparing their retention times and UV/Vis spectra with the data of 1 and 3. For the phthalocyanines 8-10 and the naphthalocyanines 11 and 12 only the C4h and D2h isomers could be separated.

Tuning of photo- and electroluminescence of new soluble, PPV-analogous short-chain compounds with naphthalene moieties

A series of oligomers analogous to poly(p-phenylenevinylene) (PPV), combining naphthalene and benzene as aromatic units, have been synthesized by a Knoevenagel reaction. By measuring UV/Vis spectra, photoluminescence (PL) and electroluminescence (EL), we studied the influence of the position of the naphthalene unit as well as the steric and electronic influences of cyano and alkyloxy substituents on the luminescent properties of these compounds.