title: Ultrafast Photoinduced Charge Separation Leading to High-Energy Radical Ion-Pairs in Directly Linked Corrole-C60 and Triphenylamine-Corrole-C60 Donor-Acceptor Conjugates.
abstract: Closely positioned donor-acceptor pairs facilitate electron- and energy-transfer events, relevant to light energy conversion. Here, a triad system TPACor-C60 , possessing a free-base corrole as central unit that linked the energy donor triphenylamine (TPA) at the meso position and an electron acceptor fullerene (C60) at the β-pyrrole position was newly synthesized, as were the component dyads TPA-Cor and Cor-C60. Spectroscopic, electrochemical, and DFT studies confirmed the molecular integrity and existence of a moderate level of intramolecular interactions between the components. Steady-state fluorescence studies showed efficient energy transfer from (1) TPA* to the corrole and subsequent electron transfer from (1) corrole* to fullerene. Further studies involving femtosecond and nanosecond laser flash photolysis confirmed electron transfer to be the quenching mechanism of corrole emission, in which the electron-transfer products, the corrole radical cation (Cor(⋅+) in Cor-C60 and TPA-Cor(⋅+) in TPACor-C60) and fullerene radical anion (C60(⋅-)), could be spectrally characterized. Owing to the close proximity of the donor and acceptor entities in the dyad and triad, the rate of charge separation, kCS , was found to be about 10(11)  s(-1), suggesting the occurrence of an ultrafast charge-separation process. Interestingly, although an order of magnitude slower than kCS , the rate of charge recombination, kCR , was also found to be rapid (kCR ≈10(10)  s(-1)), and both processes followed the solvent polarity trend DMF>benzonitrile>THF>toluene. The charge-separated species relaxed directly to the ground state in polar solvents while in toluene, formation of (3) corrole* was observed, thus implying that the energy of the charge-separated state in a nonpolar solvent is higher than the energy of (3) corrole* being about 1.52 eV. That is, ultrafast formation of a high-energy charge-separated state in toluene has been achieved in these closely spaced corrole-fullerene donor-acceptor conjugates.
authors.affiliation: Inorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Habsiguda, Hyderabad, 500007, Telangana, India.
authors.forename: Kolanu
authors.initials: K
authors.lastname: Sudhakar
authors.affiliation: Inorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Habsiguda, Hyderabad, 500007, Telangana, India.
authors.forename: Sabapathi
authors.initials: S
authors.lastname: Gokulnath
authors.affiliation: Inorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Habsiguda, Hyderabad, 500007, Telangana, India. giribabu.iict@gov.in.
authors.forename: Lingamallu
authors.initials: L
authors.lastname: Giribabu
authors.affiliation: Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton, TX, 76203-5017, USA.
authors.forename: Gary N
authors.initials: GN
authors.lastname: Lim
authors.affiliation: Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton, TX, 76203-5017, USA.
authors.forename: Tạ
authors.initials: T
authors.lastname: Trâm
authors.affiliation: Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton, TX, 76203-5017, USA. francis.dsouza@unt.edu.
authors.forename: Francis
authors.initials: F
authors.lastname: D'Souza
keywords: corrole; electron transfer; fullerenes; high-energy charge-separated species; transient absorption spectroscopy; triphenylamine