Synthesis and photodynamics of diphenylethynyl-bridged porphyrin-quinoidal porphyrin hybrids

As new donor-acceptor hybrids for energy and/or electron transfer, zinc complex and free-base of a porphyrin-quinoidal porphyrin dyad linked by a diphenylethynyl bridge were prepared via Sonogashira and subsequent Takahashi coupling reactions. The quinoidal porphyrin units have two dicyanomethylene groups at the opposite meso-positions. The UV-vis absorption spectra of the dyads were almost linear summations of the absorption spectra of each component in comparison with those of the monomeric reference compounds, indicating very weak electronic interactions between the chromophores at the ground state. Both zinc complex and free-base of the reference porphyrin exhibited fluorescence in the range of ca. 600-700 nm upon photoexcitation, while the quinoidal porphyrin monomers showed no fluorescence. The considerable quenching (more than 99%) of the porphyrin fluorescence in the dyads suggested significant electronic communications between the subunits of the excited state. The electrochemical analysis confirmed that the first oxidations of the dyads occur at the porphyrin units and the first reductions take place at the quinoidal porphyrin units. Femtosecond laser flash photolysis of the zinc dyad with photoexcitation at 393 nm showed both ultrafast (<1 ps) energy and electron transfer from the porphyrin unit to the quinoidal porphyrin one, which processes resulted in the quenching of the porphyrin fluorescence. On the other hand, the free-base dyad underwent only energy transfer.