Ph.D. Francesca Terenziani

F. Terenziani got the Laurea Degree in Chemistry in 1999 (magna cum laude), and the PhD Degree in Chemical Sciences in 2003 from Parma University. In 2003, she submitted an original research project to the European Research Council, in the framework of the Marie Curie Actions (6th European Community Framework Programme). The project, entitled “SISMA” (Supramolecular Interactions in Smart MAterials) was ranked in the highest-merit area, and was funded, allowing for a 18-months post-doc position in the Molecular and Supramolecular Photonics group (CNRS, UMR 6510), directed by Dr. Mireille Blanchard-Desce in the Rennes 1 University (France). Since November 2005 F. Terenziani joined the Dipartimento di Chimica GIAF of the Parma University as a researcher.

The research activity is mainly devoted to organic polar and/or polarizable chromophores, i.e. molecules where electron-rich groups and an electron-poor groups are linked by pi-conjugated bridges. During the PhD thesis in Parma, the effects of electron-molecular vibration coupling and of the environment on spectral properties and non-linear optical responses of these structures have been widely studied, both experimentally, by the use of spectroscopic techniques, and theoretically, by the development of original theoretical models. The post-doc research activity at University of Rennes 1 was devoted to the modeling of supramolecular structure-properties relationships in multichromophores and materials made up of polar and polarizable chromophores, and their spectroscopic characterization through linear and nonlinear (multiphoton) techniques.

Main results include the development of essential-state charge-transfer models for polar-polarizable molecules. Linear electron-vibration coupling was introduced in a non perturbative way, and important vibronic/vibrational contributions were predicted in NLO properties (static and dynamic). The predicted vibrational channel contributions to two-photon absorption were nicely confirmed by recent experimental results.
Coupling to a classical solvation mode was also added, modeling the absorption and emission solvatochromism of molecules of different symmetry (dipolar, quadrupolar, octupolar), infrared and Raman spectra, as well as time-resolved spectra. The intriguing and non trivial spectroscopic behavior of different classes of molecules was rationalized, introducing the concept of solvent-induced symmetry breaking for quadrupolar and octupolar chromophores. Results were compared with predictions from state-of-the-art quantum-chemical predictions, thanks to a collaboration with Dr. Sergei Tretiak (Los Alamos National Laboratory). Common results are also the subjet of a Review recently appeared in Advanced Materials.
Since a few years ago, much attention was devoted to the effects of electrostatic interactions on the properties of polarizable molecules, with the aim to predict the properties of crystals, films, aggregates. Arrays of chromophores with attractive or repulsive Coulomb interactions provided models for collective and cooperative phenomena and showed the limitations of the standard exciton theory. The great novelty of the proposed approach relies on the fact that the molecular (hyper)polarizability is fully and self-consistently accounted for, so that the properties of interacting chromophores can be predicted starting from the knowledge of easily accessible properties of the simple isolated chromophore (for example in solution). This theoretical “bottom-up” approach mimics the synthetic route from the molecular to the supramolecular level. The models were validated against experimental data on different series of multichromophoric assemblies and films, most of all thanks to a collaboration with the group of Dr. Blanchard-Desce. Moreover, theoretical predictions were the starting point for the design of new supramolecular systems with improved properties (see the recent publication on Angew. Chem. Int. Ed.).
As an extreme manifestation of collectivity, the possible achievement of multielectron transfer as induced by the absorption of a single photon (as the primary photoexcitation event) was predicted for clusters of attractively interacting dipolar donor-acceptor chromophores. This phenomenon is particularly attractive with respect to the efficiency of photoconversion processes.
More recently, the effects of static electric fields on the properties of dipolar, quadrupolar and octupolar chromophores was addressed. New contributions, beyond the standard Liptay approach, were found for electroabsorption spectra. The sensitivity of the emission properties of quadrupolar and octupolar chromophores to static electric fields was proposed for voltage-sensing applications, such as monitoring membrane potentials, and for voltage-tunable LEDs and white-light generation.
The concepts and approaches developed during these last years are now being applied and extended in order to model energy-transfer phenomena.

A new research area has recently been opened in the field of organic nanoparticles. Up to now we have been interested in fluorescence organic nanoparticles for their use in optical (bio)imaging. We are also intereste in the possibility to find multiexciton states in organic nanoaggregates.

Tel: +39 0521 905453
Fax: +39 0521 905556
E-mail: francesca.terenziani@unipr.it

Favourite publication

1) V. Parthasarathy, S. Fery-Forgues, E. Campioli, G. Recher, F. Terenziani, M. Blanchard-Desce, Dipolar versus Octupolar Triphenylamine-based Fluorescent Organic Nanoparticles as Brilliant One- and Two-Photon Emitters for (Bio)imaging Purpose, Small 7 (2011) 3219-3229
2) F. Terenziani, V. Parthasarathy, A. Pla-Quintana, T. Maishal, A.-M. Caminade, J.-P. Majoral, M. Blanchard-Desce, Cooperative Two-Photon Absorption Enhancement via Through-Space Interactions in Covalent Multichromophoric Compounds, Angew. Chem. Int. Ed. 48 (2009) 8691-8694
3) F. Terenziani, C. Katan, M. Blanchard-Desce, E. Badaeva, S. Tretiak, Enhanced Two-Photon Absorption of Organic Chromophores: Experimental and Theoretical Assessments, Adv. Mater. 20 (2008) 4641-4678 (Review; Cover Paper)
4) F. Terenziani, M. Morone, S. Gmouh, M. Blanchard-Desce, Linear and Two-Photon Absorption Properties of Interacting Polar Chromophores: Standard and Unconventional Effects, ChemPhysChem 7 (2006) 685-696. (cover article)
5) A. Painelli, F. Terenziani, Multielectron transfer in clusters of polar-polarizable chromophores, J. Am. Chem. Soc. 125, 5624 (2003).

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