• Energy Research

AbstractA tetrahedral shape‐persistent molecule equipped with four terpyridine ligands can form an oligomeric structure upon complexation with metal ions, in which two terpyridine units are intermolecularly connected via a metal ion. The most interesting results were obtained upon binding of lanthanide ions, whose luminescence is sensitized by the ligand. In particular, dual luminescent probes were obtained upon concomitant complexation of two different lanthanide ions, such as EuIII and NdIII.

The photocatalytic mechanism reported in a recent Communication to produce the radical anion of pyrenes postulates a highly endergonic electron transfer process. An analysis of the thermodynamics is reported together with the proposal of an alternative thermodynamically feasible mechanism.

Photoluminescence of silicon nanocrystals (SiNCs) in the presence of a series of quinone electron acceptors and ferrocene electron donors is quenched by oxidative and reductive electron transfer dynamic processes, respectively. The rate of these processes is investigated as a function of (a) the thermodynamic driving force of the reaction, by changing the reduction potentials of the acceptor or donor molecules, (b) the dimension of SiNCs (diameter = 3.2 or 5.0 nm), (c) the surface capping layer on SiNCs (dodecyl or ethylbenzene groups), and (d) the solvent polarity (toluene vs dichloromethane). The results were interpreted within the classical Marcus theory, enabling us to estimate the position of the valence and conduction bands, as well as the reorganization energy (particularly small, as expected for quantum dots) and electronic transmission coefficients. The last parameter is in the range 10–5–10–6, demonstrating the nonadiabaticity of the process, and it decreases upon increasing the SiNC dimensions:...

Silicon (Si) nanocrystals are relatively strong light emitters, but are weak light absorbers as a result of their indirect band gap. One way to enhance light absorption is to functionalize the nanocrystals with chromophores that are strong light absorbers. By designing systems that enable efficient energy transfer from the chromophore to the Si nanocrystal, the brightness of the nanocrystals can be significantly increased. There have now been a few experimental systems in which covalent attachment of chromophores, efficient energy transfer and significantly increased brightness have been demonstrated. This review discusses progress on these systems and the remaining challenges.

AbstractA shape‐persistent molecule, featuring four bipyridinium units, has been synthesized that upon reduction undergoes intermolecular pimerization because of the rigid architecture of the molecule. The pimerization process has been investigated by a variety of techniques, such as absorption measurements, EPR spectroscopy, as well as gamma and pulse radiolysis, and compared with the behavior of a model compound. Computational studies have also been performed to support the experimental data. The most interesting feature of the tetramer is that pimerization occurs only above a threshold concentration of monoreduced species, on the contrary to the model compound. Furthermore, there is an increase of the apparent pimerization constant by increasing the concentration of reduced bipyridinium units. These results have been interpreted by the fact that pimerization is favored in the tetrahedrally shaped molecule because of a cooperative mechanism. Each multiply reduced molecule can indeed undergo multiple intermolecular interactions that enhance the stabilization of the system, also leading to hierarchical supramolecular growth. The resulting supramolecular system formed by such intermolecular pimerization should exhibit a diamond‐like structure, as suggested by a simplified modeling approach. The intermolecular nature of the pimerization process occurring in the tetramer has been demonstrated by measuring the corresponding bimolecular rate constant by pulsed radiolysis experiments.

Graphene-metal composites have potential as novel catalysts due to their unique electrical properties. Here, we report the synthesis of a composite material comprised of monodispersed platinum nanoparticles on high-quality graphene obtained by using two different exfoliation techniques. The material, prepared via an easy, low-cost and reproducible procedure, was evaluated as an electrocatalyst for the hydrogen evolution reaction. The turnover frequency at zero overpotential (TOF0 in 0.1 m phosphate buffer, pH 6.8) was determined to be approximately 4600 h(-1). This remarkably high value is likely due to the optimal dispersion of the platinum nanoparticles on the graphene substrate, which enables the material to be loaded with only very small amounts of the noble metal (i.e., Pt) despite the very highly active surface. This study provides a new outlook on the design of novel materials for the development of robust and scalable water-splitting devices.

A hexathiobenzene molecule carrying six terpyridine (tpy) units at the periphery has been designed to couple the aggregation induced phosphorescence, displayed by the core in the solid state, to the metal binding properties of the tpy units. Upon Mg(2+) complexation in THF solution, phosphorescence of the hexathiobenzene core is turned on. Metal ion coordination yields the formation of a supramolecular polymer which hinders intramolecular rotations and motions of the core chromophore, thus favoring radiative deactivation of the luminescent excited state. Upon excitation of the [Mg(tpy)2](2+) units of the polymeric structure, sensitization of the core phosphorescence takes place with >90% efficiency. The light-harvesting polymeric antenna can be disassembled upon fluoride ion addition, thereby switching off luminescence and offering a new tool for fluoride ion sensing. This unique system can, thus, serve as cation or anion sensor.