Synthesis, characterization and photophysical properties of ferrocenyl and mixed sandwich cobaltocenyl ester linked meso-triaryl corrole dyads

摘要

We report here the design and synthesis of corrole-metallocene dyads consisting of a metallocene (either ferrocene (Dyad 1) or mixed sandwich eta(5)-[C5H4(COOH)]Co(eta(4)-C4Ph4) (Dyad 2)) connected via an ester linkage at meso phenyl position. Both the dyads were characterized by H-1 NMR, MALDI-TOF, UV-visible, fluorescence spectroscopies (steady-state, picosecond time-resolved), femtosecond transient absorption spectroscopy (fs-TA) and electrochemical methods. The absorption spectra of these dyads showed slight broadening and splitting of the Soret band that indicates a weak ground state interaction between the corrole macrocycle and metallocene part of the present donor-acceptor (D-A) system. However, in both the dyad systems, fluorescence emission of the corrole was quenched in polar solvents as compared to its parent compound 10-(4-hydroxyphenyl)-5,15-bis(pentafluorophenyl) corrole (Ph-Corr). The quenching was more pronounced in ferrocene derivatives than in cobaltocenyl derivatives. Transient absorption studies confirm the absence of photoinduced electron transfer from metallocene to correl for these dyad systems and the quenching of singlet state of corrole is found to enhance intersystem crossing due to heavy atom effect.