Electronic structure and optical properties of charged oligofluorenes studied by VIS/NIR spectroscopy and time-dependent density functional theory.

The electronic structure and optical properties of charged oligofluorenes were studied experimentally and theoretically. Measurements of the optical absorption spectra of charged oligofluorenes in dilute solutions have been performed by using the pulse radiolysis technique. In addition, optical absorption spectra of radical cations and anions in a solid matrix were measured after gamma-irradiation at 77 K.

Synthesis and energy-transfer properties of hydrogen-bonded oligofluorenes.

A set of fluorene oligomers has been synthesized by stepwise palladium-catalyzed (Suzuki) couplings of fluorene monomers. Ureidopyrimidinones (UPy), functional groups that can dimerize via quadruple hydrogen bonds, were attached to both ends of the oligofluorenes. The resulting bis-UPy-terminated oligomers self-assemble into supramolecular chain polymers.

Interfacial electron-transfer kinetics of ferrocene through oligophenyleneethynylene bridges attached to gold electrodes as constituents of self-assembled monolayers: observation of a nonmonotonic distance dependence.

The standard heterogeneous electron-transfer rate constants (k(n)0) between substrate gold electrodes and the ferrocene redox couple attached to the electrode surface by variable lengths of substituted or unsubstituted oligophenyleneethynylene (OPE) bridges as constituents of mixed self-assembled monolayers were measured as a function of temperature. The distance dependences of the unsubstituted OPE standard rate constants and of the preexponential factors (An) obtained from an Arrhenius analysis of the unsubstituted OPE k(n)0 versus temperature data are not monotonic. This surprising result, together with the distance dependence of the substituted OPE preexponential factors, may be assessed in terms of the likely conformational variability of the OPE bridges (as a result of the low intrinsic barrier to rotation of the phenylene rings in these bridges) and the associated sensitivity of the rate of electron transfer (and, hence, the single-molecule conductance which may be estimated using An) through these bridges to the conformation of the bridge.

Synthesis and characterization of a discotic uranium-containing liquid crystal.

The synthesis of several UO(2)-alaskaphyrin derivatives functionalized with aliphatic chains is described. These compounds are found to be liquid-crystalline and form columnar mesophases, as judged from polarizing optical microscopy studies, and represent the first uranium-containing discotic mesogens.

The first liquid-crystalline, expanded porphyrins.

Aliphatic derivatives of hydrazinophyrin, a new type of tetrapyrrolic macrocycle prepared by the condensation of 2,5-diformylpyrroles with hydrazine, exhibit liquid crystalline properties as judged from polarising optical microscopy; these hydrazinophyrins appear to be the first mesogens derived from an expanded porphyrin core.