Excited Charge Separation in a π-Interacting Phenothiazine-Zinc Porphyrin-Fullerene Donor-Acceptor Conjugate.

We have designed, synthesized, and characterized a donor-acceptor triad, SPS-PPY-C60, that consists of a π-interacting phenothiazine-linked porphyrin as a donor and sensitizer and fullerene as an acceptor to seek charge separation upon photoexcitation. The optical absorption spectrum revealed red-shifted Soret and Q-bands of porphyrin due to charge transfer-type interactions involving the two ethynyl bridges carrying electron-rich and electron-poor substituents. The redox properties suggested that the phenothiazine-porphyrin part of the molecule is easier to oxidize and the fullerene part is easier to reduce. DFT calculations supported the redox properties wherein the electron density of the highest molecular orbital (HOMO) was distributed over the donor phenothiazine-porphyrin entity while the lowest unoccupied molecular orbital (LUMO) was distributed over the fullerene acceptor. TD-DFT studies suggested the involvement of both the S2 and S1 states in the charge transfer process. The steady-state emission spectrum, when excited either at porphyrin Soret or visible band absorption maxima, revealed quenched emission both in nonpolar and polar solvents, suggesting the occurrence of excited state events. Finally, femtosecond transient absorption spectral studies were performed to witness the charge separation by utilizing solvents of different polarities. The transient data was further analyzed by GloTarAn by fitting the data with appropriate models to describe photochemical events. From this, the average lifetime of the charge-separated state calculated was found to be 169 ps in benzonitrile, 319 ps in dichlorobenzene, 1.7 ns in toluene for Soret band excitation, and ∼320 ps for Q-band excitation in benzonitrile.

Novel phosphorus(V) tetrabenzotriazacorroles: synthesis, characterization, optical, electrochemical, and femtosecond nonlinear optical studies.

A series of three novel tetrabenzotriazacorroles (TBCs) designed with an alkyl substituent tert-butyl group (TBC-tert), an electron donor phenothiazine group (TBC-PTZ) and an energy donor carbazole group (TBC-CBZ) on the peripheral position with phosphorus metal in the cavity have been synthesized. All three compounds were characterized using various spectroscopic techniques and we assessed their femtosecond third-order nonlinear optical (NLO) properties. TBCs exhibit the properties of both phthalocyanines and corroles as they are derived from parent phthalocyanines. The optical studies revealed a new band at ∼450 nm, which was absent in the parent phthalocyanine molecules, and all three compounds obeyed Beer-Lambert's law. Singlet-state quantum yields were measured in different solvents and were found to be in the range of 0.3 to 0.6 for TBC-tert, 0.21 to 0.25 in the case of TBC-PTZ and 0.31 to 0.41 for TBC-CBZ. Time-resolved fluorescence studies revealed lifetimes in the ns regime (typically few ns). The redox properties of the TBCs suggest that they are easier to oxidize and harder to reduce and exhibit multiple oxidation and reduction potentials. Using the Z-scan technique, the third-order NLO properties were investigated with kilohertz and megahertz repetition rate femtosecond pulses at 800 nm. We report the first observation of strong three-photon absorption in these molecules with coefficients of ∼10-22 cm3 W-2 (∼10-13 cm3 W-2) with kHz (MHz) repetition rate fs pulse excitation.