Chiara Marinzi

Di-branched di-anchoring organic dyes for dye-sensitized solar cells

The first examples of di-branched di-anchoring organic sensitizers were synthesized and used in dye-sensitized solar cells leading to red-shifted IPCE maxima and increased photocurrent when compared to the corresponding mono-branched mono-anchoring dye, yielding power conversion efficiency of 5.7% (4.9% with ionic liquid electrolyte) with enhanced stability under 1 sun conditions from the di-anchoring groups.

Panchromatic ruthenium sensitizer based on electron-rich heteroarylvinylene π-conjugated quaterpyridine for dye-sensitized solar cells

The first example of a heteroarylvinylene π-conjugated quaterpyridine Ru(II) sensitizer (N1044) was synthesized and used in dye-sensitized solar cells; the dye has an effective panchromatic absorption band, covering the entire visible spectrum up to the NIR region, and superior electrochemical characteristics (HOMO/LUMO and bandgap energies) with respect to previous representative Ru(II) bi- and quaterpyridine sensitizers. A record IPCE curve ranging from 360 to 920 nm has been measured with a maximum of 65% at 646 nm and still 33% efficiency at 800 nm; this leads to substantially increased photocurrent (19.2 mA cm(-2)) when compared to the prototype N719 Ru(II) sensitizer.

Design, Synthesis and Biological Evaluation of Sugar-Derived Ras Inhibitors

The design and synthesis of novel Ras inhibitors with a bicyclic scaffold derived from the natural sugar D‐arabinose are presented. Molecular modelling showed that these ligands can bind Ras by accommodating the aromatic moieties and the phenylhydroxylamino group in a cavity near the Switch II region of the protein. All the synthetic compounds were active in inhibiting nucleotide exchange on p21 human Ras in vitro, and two of them selectively inhibited Ras‐dependent cell growth in vivo.

Dimers of quadrupolar chromophores in solution: electrostatic interactions and optical spectra.

Two dimers of a heteroaromatic quadrupolar (acceptor-donor-acceptor) chromophore have been synthesized with different interchromophoric distances. Optical spectra of dimers in solution show a red shift of the linear absorption band upon decreasing the interchromophore distance, while fluorescence and two-photon absorption spectra are only marginally affected by the interactions. A bottom up approach is adopted to describe the spectra: via a detailed spectroscopic analysis of the monomeric species in solution, we define an essential-state model for the isolated chromophore and use this information to set up a model for the dimers also accounting for interchromophore electrostatic interactions. To discriminate between static screening governed by the static dielectric constant and dynamical screening at optical frequencies, we first solve the problem in the mean-field approximation and then define the excitonic Hamiltonian on the resulting best excitonic basis. Along this line, the evolution of spectral properties with the interchromophore distance is properly rationalized.

Emission properties of artificial opals infiltrated with a heteroaromatic quadrupolar dye

Artificial opals are a simple and cheap playground to manipulate the propagation of light. The interest in these kind of photonic crystals is further increased by the possibility to be infiltrated with highly polarisable media like organic semiconductors, i.e. conjugated polymers, push-pull molecules and multipolar chromophores. In this work, we report on the optical properties of polystyrene opals infiltrated with a heteroaromatic quadrupolar derivative endowed with strong nonlinear optical properties (two-photon absorption) in solution. The insertion of tris(ethylene glycol)monomethyl ether chains on the conjugated skeleton allows the molecule to be soluble in water, a non-solvent for polystyrene. This condition is fundamental in order to attempt opal infiltration. Variable angle transmittance and photoluminescence spectroscopy are used to characterize the system. The bathochromic shift of the opal stop band upon immersion in the chromophore solution confirms that the infiltration process easily takes place preserving a dielectric contrast suitable for further investigations. Photoluminescence spectra recorded at different emission angle with respect to the normal of the sample for both the chromophore solution and opals infiltrated with such solution show interesting characteristics. The presence of opal modifies the chromophore emission spectrum by filtering the light for wavelengths corresponding to those of the stop band and according to its dispersion.

One- and two-photon absorption and emission properties of heteroaromatic bichromophores

We present the design, synthesis, and characterization of a class of heteroaromatic bichromophores in order to investigate intermolecular interactions and their effect on optical and nonlinear optical properties. As a design strategy we have linked two dipolar or quadrupolar units through a non-conjugated alkyl chain. The two units are connected either through their donor or their acceptor end-groups. This study represents a first step towards the design of bi- and multichromophoric systems with optimized NLO responses in order to exploit collective and cooperative effects from interchromophore interactions.