Expanding the Subporphyrazine Chromophore by Conjugation of Phenylene and Vinylene Substituents: Rainbow SubPzs

Article abstract of DOI:10.1021/acs.joc.9b02658

The efficiency of the vinylene moiety as a linker to intercommunicate the subporphyrazine (SubPz) core with other chromophores and redox active systems has been examined. In addition, different substitution patterns for hexaarylated SubPzs have been explored in order to control the absorption, fluorescence, and redox properties independently of one another. Besides X-ray crystallography, complete spectroscopic and electrochemical characterizations have been performed, and the conclusions have been supported by density functional theory calculations. The absorption and emission profiles, as well as the organization of the macrocycles in the crystalline state, are strongly determined by the substitution pattern. Within the hexaarylated family, para-substitution with electron-rich moieties (i.e., phenylene or ether) red-shifts both the SubPz absorption and emission bands. Progressive fading of these effects upon extending the oligophenylene branches from one to three units evidences the less efficient electronic delocalization over the phenyl ends as the oligophenylene branch is enlarged. Contrasting, meta-substitution produces little variation or blue shift of the SubPz Q-band, while bathochromic shifts are always observed for the emission bands. In hexavinylene-SubPzs, peripheral vinylene moieties adopt a coplanar configuration with the aromatic SubPz core, resulting in a π-extended chromophore that preserves the unique electronic tunability of SubPzs. This is reflected by the strong alteration of the SubPz electronic properties produced by phenyl and biphenyl moieties attached to the vinylene ends.