Subphthalocyanine–tetracyanobuta-1,3-diene–aniline conjugates: stereoisomerism and photophysical properties† †This article is dedicated to Prof. Michael R. Wasielewski on the occasion of his 70th birthday. ‡ ‡Electronic supplementary information (ESI) available: Procedures for synthesis, characterization data, and supplementary figures. See DOI: 10.1039/c9sc03970h

• Published in: Chemical science (Cambridge) Vol. 10; no. 48; pp. 10997 - 11005
• Main Authors: Winterfeld, Kim A., Lavarda, Giulia, Guilleme, Julia, Guldi, Dirk M., Torres, Tomás, Bottari, Giovanni
• Format: Journal Article
• Language: English
• Published: Royal Society of Chemistry 19.09.2019
• Subjects: Chemistry
• DOI: 10.1039/c9sc03970h
• ISSN: 2041-6520

We report the stereoisomerism and physicochemical properties of two novel electron donor–acceptor conjugates based on subphthalocyanines decorated at their peripheral, or peripheral/axial positions with multiple tetracyanobutadiene–aniline moieties. Two subphthalocyanines (SubPcs) decorated at their peripheral (SubPc 1 ) or peripheral and axial (SubPc 2 ) positions with tetracyanobuta-1,3-diene (TCBD)–aniline moieties have been prepared as novel electron donor–acceptor (D–A) conjugates. In 1 and 2 , the multiple functionalization of C 3 -symmetric SubPcs by TCBD moieties, each of them having a chiral axis, results in the formation of several stereoisomers. Variable temperature 1 H-NMR studies in chlorinated solvents suggest that these latter species, which are detected at low temperatures, rapidly interconvert – on the NMR timescale – into each other at room temperature. Beside their unique structural and stereochemical features, 1 and 2 present interesting physicochemical properties. Steady-state absorption and fluorescence, as well as electrochemical studies on 1 and 2 clearly point to an important degree of electronic communication between the SubPc, the TCBD and the aniline subunits. Moreover, in both derivatives, photoexcitation of the SubPc moiety yields charge transfer products involving the electron-rich SubPc moiety and the electron-withdrawing TCBD fragment. Interestingly, such polarized excited state species evolve in 1 and 2 in different ways. While in the former compound, it directly decays to the ground state, the fourth axial TCBD moiety in 2 leads to the formation of an intermediate fully charge separated state prior to the ground state deactivation.