Transient electrochemistry: beyond simply temporal resolution.

Some physicochemical intrigues for which transient electrochemistry was necessary to solve the problem are summarized in this feature article. First, we highlight the main constraints to be aware of to access to low time scales, and particularly focus on the effects of stray capacitances. Then, the electron transfer rate constant measured for redox molecules in a self-assembled monolayer configuration is compared to the conductance measured through the same systems, but at the single molecule level. This evidences strong conformational changes when molecules are trapped in the nanogap created between both electrodes. We also report about dendrimers, for which a short electrochemical perturbation induces creation of a diffusion layer within the molecule, allowing the electron hopping rate to be measured and analyzed in terms of molecular motions of the redox centers. Finally, we show that transient electrochemistry provides also useful information when coupled to other methodologies. For example, when an ultrasonic field drives very fast movements of a bubble situated above the electrode surface, the motion can be detected indirectly through a modification of the diffusion flux. Another field concerns pulse radiolysis, and we describe how the reactivity (at the electrode or within the solution) of radicals created by a radiolytic pulse can be quantified, widening the possibilities of electrochemistry to operate in biological media.

A photoresponsive graphene oxide-C60 conjugate.

An all-carbon donor-acceptor hybrid combining graphene oxide (GO) and C60 has been prepared. Laser flash photolysis measurements revealed the occurrence of photoinduced electron transfer from the GO electron donor to the C60 electron acceptor in the conjugate.

A liquid crystalline supramolecular complex of C60 with a cyclotriveratrylene derivative

Cyclotriveratrylene (CTV) derivatives substituted with 9 (1) or 18 (2) long alkyl chains have been prepared. Whereas no liquid crystalline behavior has been observed for 1, the CTV derivative 2 has mesomorphic properties. Indeed, at room temperature compound 2 exhibits a nematic phase characterized by cybotactic groups with a local lamello-columnar order. Both CTV derivatives 1 and 2 are able to form supramolecular complexes with C60 in the solid state. In both cases, the 2:1 host-guest species have been obtained as brown compounds. No liquid crystalline behavior was observed for the supramolecular complex [C60 is included in (1)2]. In contrast, observation of the brown product obtained from C60 and the CTV derivative 2 directly after preparation by polarized optical microscopy revealed a fluid birefringent phase at room temperature. When the sample is heated above 70 degrees C, the birefringence of the texture under the microscope disappears and the X-ray diffraction pattern is transformed into a pattern characteristic of a cubic phase. For the first time in thermotropic liquid crystals, the space group of this cubic phase can be assigned as I4(1)32.

Fullerodendrimers: a new class of compounds for supramolecular chemistry and materials science applications

Encapsulation of a fullerene sphere in the middle of a dendritic structure prevents unfavorable effects of the C60 unit, such as aggregation or steric hindering. Such fullerodendrimers appear to be promising compounds for materials science applications. On the other hand, fullerodendrons with peripheral C60 subunits or containing a C60 sphere at each branching unit appear to be versatile building blocks for the preparation of fullerene-rich macromolecules with intriguing properties.

Investigations of Thin Films with Amphiphilic Dendrimers Bearing Peripheral Fullerene Subunits.

In spite of a molecular mass of 7704.6 g mol(-1), third-generation compound G3 (shown schematically; Z=C(8)H(17)) is able to form stable Langmuir films. In a systematic study, the amphiphilic properties of the corresponding dendrimers of first (G1) and second generation (G2), with one and two peripheral fullerene units, respectively, were investigated and a model could be proposed for the multilayer films obtained from G1.

A Copper(I) Bis-phenanthroline Complex Buried in Fullerene-Functionalized Dendritic Black Boxes.

Virtual inaccessibility to external contact was revealed by electrochemical investigations for a bis(1,10-phenanthroline)copper(I) core embedded in dendrimers with up to 16 peripheral fullerene units (shown schematically). With increasing numbers of fullerene units, less and less light is available to the core, and the small quantity of light energy that reaches the central Cu(I) complex is returned to the external fullerenes by energy transfer-the central core is buried in a dendritic black box.