Cyclization of Pyrene Oligomers: Cyclohexa-1,3-pyrenylene.

First synthesis of the macrocycle cyclohexa(1,3-pyrenylene) is achieved in six steps starting with pyrene, leading to a non-aggregating highly twisted blue-light-emitting material. The cyclodehydrogenation of the macrocycle offers a promising synthesis route to holey-nanographene.

Deep blue polymer light emitting diodes based on easy to synthesize, non-aggregating polypyrene.

Thorough analyses of the photo- and devicephysics of poly-7-tert-butyl-1,3-pyrenylene (PPyr) by the means of absorption and photoluminescence emission, time resolved photoluminescence and photoinduced absorption spectroscopy as well as organic light emitting devices (OLEDs) are presented in this contribution. Thereby we find that this novel class of polymers shows deep blue light emission as required for OLEDs and does not exhibit excimer or aggregate emission when processed from solvents with low polarity. Moreover the decay dynamics of the compound is found to be comparable to that of well blue emitting conjugated polymers such as polyfluorene.

Tunneling versus hopping in mixed-valence oligo-p-phenylenevinylene polychlorinated bis(triphenylmethyl) radical anions.

Radical anions 1(-•)-5(-•), showing different lengths and incorporating up to five p-phenylenevinylene (PPV) bridges between two polychlorinated triphenylmethyl units, have been prepared by chemical or electrochemical reductions from the corresponding diradicals 1-5 which were prepared using Wittig-Horner-type chemistry. Such radical anions enabled us to study, by means of UV-vis-NIR and variable-temperature electron spin resonance spectroscopies, the long-range intramolecular electron transfer (IET) phenomena in their ground states, probing the influence of increasing the lengths of the bridges without the need of using an external bias to promote IET. The temperature dependence of the IET rate constants of mixed-valence species 1(-•)-5(-•) revealed the presence of two different regimes at low and high temperatures in which the mechanisms of electron tunneling via superexchange and thermally activated hopping are competing.

Changes in electronic couplings of mixed-valence systems due to through-space intramolecular interactions.

The strength of the electronic interactions between the two redox moieties in fullerene-substituted mixed-valence bis(ferrocenylethynyl)ethene derivatives is modulated by the through-space intramolecular electronic interactions of C(60) with the bridging conjugated system.

Molecular and supramolecular C60-oligophenylenevinylene conjugates.

Fullerene derivatives are attractive building blocks for the preparation of molecular and supramolecular photoactive devices. As a part of this research, combination of C60 with oligophenylenevinylene (OPV) subunits has generated significant research efforts. These results are summarized in the present account to illustrate the current state-of-the-art of fullerene chemistry for the development of new photoactive materials.

Synthesis and excited state properties of a [60]fullerene derivative bearing a star-shaped multi-photon absorption chromophore.

The synthesis and excited state properties of a compound assembling C60 with a new multi-photon absorption chromophore are reported.

Influence of bridge topology and torsion on the intramolecular electron transfer.

To study molecules able to act as good "molecular wires", intramolecular electron transfer between two triphenylmethyl redox centers connected by bridges with different topologies and substituents have been studied in solution, both by UV-Vis-NIR and EPR spectroscopies. The synthetic methodology used allows a complete control of the geometry of polychlorotriphenylmethyl diradicals 1 and 2, which have para and meta topologies, respectively, as well as of their E/Z isomerism. This fact is used to show the influence of the different topologies in the ease of electron transfer, which is larger for the para than for the meta isomer where a small or negligible electronic coupling is observed.

Pyrazolino[60]fullerene-oligophenylenevinylene dumbbell-shaped arrays: synthesis, electrochemistry, photophysics, and self-assembly on surfaces.

Symmetrically substituted oligophenylenevinylene (OPV) derivatives bearing terminal p-nitrophenylhydrazone groups have been prepared and used for the synthesis of dumbbell-shaped bis(pyrazolino[60]fullerene)-OPV systems. In these triad arrays, the OPV-type fluorescence is dramatically quenched as a consequence of ultrafast OPV-->C60 singlet energy transfer. In its turn the fullerene singlet state is quenched by pyrazoline-->C60 electron transfer, in line with the behavior of the corresponding reference fullerene molecule.

A supramolecular cup-and-ball C60-porphyrin conjugate system.

In addition to the ammonium-crown ether recognition, pi-stacking interactions between the C60 sphere and the porphyrin moiety have been evidenced in a supramolecular complex obtained from a porphyrin-crown ether conjugate and a fullerene derivative bearing an ammonium unit.