Symmetrically Functionalized Copper and Silver Corrole-Bis-Tetracyanobutadiene Push-Pull Conjugates: Efficient Population of Triplet States via Charge Transfer.

Copper and silver tritolylcorroles (TTC) are symmetrically functionalized to carry two tetracyanobutadiene (TCBD) entities via [2+2] cycloaddition-retroeletrocyclization reaction involving ethynyl functionalized corroles with an electron acceptor, tetracyanoethylene (TCNE) in excellent yields, as the first examples of corrole-TCBD push-pull systems. The strong push-pull effect resulted in charge polarization in the ground state resulting in a considerable hypsochromic shift of the spectrum extending it into the near-IR region. Electrochemical studies coupled with computational studies revealed considerable interactions between the two TCBD entities via the corrole π-system and the degree of such interactions was found to depend on the metal ion present in the corrole cavity. Energy considerations suggested charge transfer (CT) from the S or vibrationally hot S state but not the relaxed S state in the case of CuTTC(TCBD) while CT to occur from all these states in the case of AgTTC(TCBD) . Additionally, the high-energy CT states populate the low-lying triplet states. Systematic femtosecond pump-probe studies provided the ultimate proof for the occurrence of excited CT as a function of excitation wavelength followed by the efficient population of the triplet states. The present study brings out the significance of charge transfer in efficiently populating the triplet states in rather unusual copper and silver corroles carrying two TCBD entities.