Christophe Bucher

This study presents the synthesis, the spectroscopic and electrochemical properties of new bis‐ and tetra‐substituted azaboron‐dipyrromethene (aza‐BODIPY) dyes substituted by different electron donating groups connected to the aza‐BODIPY core through a thiophene unit. In line with theoretical calculations, experimental measurements point out the positive impact of the thiophene group that behave as a secondary donor group leading to an enhancement of the intramolecular charge transfer process in comparison to previously reported aza‐BODIPY dyes. This heterocycle has also been found to tune the oxidative potential and to stabilize the electro‐generated species.

CF 3 ‐substituted porphyrins have attracted increasing interest over the past decade. However, the number of examples reported in the literature remains quite limited and much remains to be done to understand the properties and reactivity of these molecules. We are now reporting on the synthesis of a series of free base porphyrins incorporating one, two and three CF 3 substituents, including the 5,10,15‐tris(CF 3 ) substituted porphyrin which has never been described before. We have also carried out detailed electrochemical and spectroscopic analyses aiming at assessing the electron‐withdrawing properties of the CF 3 substituents compared to the widely used C 6 F 5 . Our studies led us to propose an interpretation of the quite unusual electrochemical signature of these molecules featuring three successive one‐electron reduction waves.