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Charge-Separation in Panchromatic, Vertically Positioned Bis(donorstyryl)BODIPY – Aluminum(III) Porphyrin – Fullerene Supramolecular Triads

Abstract

Three, broad band capturing, vertically aligned supramolecular triads, R2-BDP-AlPorF3Im-C60 [R = H, styryl (C2H2-Ph), C2H2-TPA (TPA = triphenylamine);  = coordinate bond], are constructed using BODIPY derivative (BDP, BDP-Ph2 or BDP-TPA2), 5,10,15,20-tetrakis(3,4,5-trifluorophenyl)aluminum(III) porphyrin (AlPorF3) and fullerene (C60) entities. The C60 and BDP units are bound to the Al center on opposite faces of the porphyrin; the BDP derivative through a covalent axial bond using a benzoate spacer, and the C60 through a coordination bond via an appended imidazole. Owing to the bisstyryl functionality on BDP, the constructed dyads and triads exhibited panchromatic light capture. Due to the diverse absorption and redox properties of the selected entities, it was possible to demonstrated excitation wavelength dependent photochemical events. In the case of BDP-AlPorF3 dyad, selective excitation of BDP resulted in singlet-singlet energy transfer to AlPorF3 (kEnT = 1.0 x 1010 s-1). On the other hand, excitation of AlPorF3 entity in BDP-AlPorF3Im-C60 triad, revealed charge separation leading to BDP-(AlPorF3)•–(C60)−• charge separated state (kCS = 2.43 x 109 s-1). In the case of Ph2-BDP-AlPorF3 dyad, energy transfer from 1AlPorF3* to 1(Ph2-BDP)* was witnessed (kEnT = 1.0 x 1010 s-1), however, upon assembling the supramolecular triad, (Ph2-BDP)-AlPorF3Im-C60, electron transfer from 1AlPorF3* to C60 (kCS = 3.35 x 109 s-1) followed by hole shift (kHS = 1.00 x 109 s-1) to Ph2-BDP was witnessed. Finally, in the case of TPA2-BDP-AlPorF3Im-C60 triad, only electron transfer leading to (TPA2-BDP)•-AlPorF3Im-(C60)−• charge separated state and no energy transfer was observed. The facile oxidation of Ph2-BDP and TPA2-BDP compared to AlPorF3 in the latter two triads facilitated charge separation through either an electron migration or hole transfer mechanism depending upon initial excitation. The charge-separated states in these triads persisted for about 20 ns.

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Publication details

The article was received on 17 Aug 2018, accepted on 11 Oct 2018 and first published on 12 Oct 2018


Article type: Paper
DOI: 10.1039/C8NR06649C
Citation: Nanoscale, 2018, Accepted Manuscript
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    Charge-Separation in Panchromatic, Vertically Positioned Bis(donorstyryl)BODIPY – Aluminum(III) Porphyrin – Fullerene Supramolecular Triads

    N. Zarrabi, C. Obondi, G. N. Lim, S. Seetharaman, B. G. Boe, F. DSouza and P. K. Poddutoori, Nanoscale, 2018, Accepted Manuscript , DOI: 10.1039/C8NR06649C

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