Prediction of the Synthesis of Spiro Derivatives by Double Intramolecular Aromatic Electrophilic Substitution Using Reactivity Indices.

The synthesis of heterocyclic spirobifluorene (SBF) analogs generally requires long and complicated synthetic pathways. Despite this synthetic effort, such structural modification allows the (opto)electronic properties of this remarkable three-dimensional node to be tuned especially for molecular electronic applications. For this reason, the development of a simple, robust, and efficient synthetic methodology to introduce various heterocycles in place of classical phenyl rings in the spirofluorene motif is highly and timely desirable. In this context, we describe herein our efforts to develop a straightforward and efficient synthesis leading to replacement of 2 phenyl rings by various heterocycles in spiro compounds from 2,2'-dibromobenzophenone. As the same procedure to form fully heterocyclic compounds failed, an original theoretical approach based mainly on the uncommon Fukui dual function was developed in order to determine clearly the limitation of this strategy and provide an efficient predictive tool. Indeed, such calculation allows prediction of the thermodynamic and kinetic aspects of the synthesis of spiro derivatives using a double aromatic electrophilic substitution. If this procedure reproduces well our experimental results focused on (heterocyclic) SBF compounds, it can be certainly adapted and generalized to other intramolecular substitutions.

Push-Pull Triphenylamine Chromophore Syntheses and Optoelectronic Characterizations.

A series of push-pull molecules combining a diarylamine donor block with various electron-acceptor units through phenylthienyl (PT) and bithienyl (TT) π-conjugating spacers have been synthesized. Optical and electrochemical results, supported by theoretical calculations, show that the electronic properties of the molecules can be modulated by varying the strength of the acceptor group and/or the structure of the conjugating spacer. As a first evaluation of the potential of these compounds as donors in organic solar cells (OSC), simple planar heterojunction (PHJ) prototypes using fullerene C60 as electron acceptor have been fabricated. Most OSCs exhibit analogous photoconversion efficiencies in the 1.5-2 % range. Their characteristics are discussed in terms of structure-properties relationships.