Photoinduced charge separation in three-layer supramolecular nanohybrids: fullerene-porphyrin-SWCNT
D'Souza, Francis Das, Sushanta K. Sandanayaka, Atula S. D. Subbaiyan, Navaneetha K. Gollapalli, Deviprasad R. Zandler, Melvin E. Wakahara, Takatsugu Ito, Osamu
D'Souza, Francis
Das, Sushanta K.
Sandanayaka, Atula S. D.
Subbaiyan, Navaneetha K.
Gollapalli, Deviprasad R.
Zandler, Melvin E.
Wakahara, Takatsugu
Ito, Osamu
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2012-12-14
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D'Souza F, SK Das, AS Sandanayaka, NK Subbaiyan, DR Gollapalli, ME Zandler, T Wakahara, and O Ito. 2012. "Photoinduced charge separation in three-layer supramolecular nanohybrids: fullerene-porphyrin-SWCNT.". Physical Chemistry Chemical Physics : PCCP. 14 (8): 2940-50.
Abstract
Photoinduced charge separation processes of three-layer supramolecular hybrids, fullerene-porphyrin-SWCNT, which are constructed from semiconducting (7,6)- and (6,5)-enriched SWCNTs and self-assembled via pi-pi interacting long alkyl chain substituted porphyrins (tetrakis(4-dodecyloxyphenyl)porphyrins; abbreviated as MP(alkyl)(4)) (M = Zn and H-2), to which imidazole functionalized fullerene[60] (C(60)Im) is coordinated, have been investigated in organic solvents. The intermolecular alkyl-pi and pi-pi interactions between the MP (alkyl)(4) and SWCNTs, in addition, coordination between C(60)Im and Zn ion in the porphyrin cavity are visualized using DFT calculations at the B3LYP/3-21G(*) level, predicting donor-acceptor interactions between them in the ground and excited states. The donor-acceptor nanohybrids thus formed are characterized by TEM imaging, steady-state absorption and fluorescence spectra. The time-resolved fluorescence studies of MP(alkyl)(4) in two-layered nanohybrids (MP(alkyl)(4)/SWCNT) revealed efficient quenching of the singlet excited states of MP(alkyl)(4) ((MP)-M-1*(alkyl)(4)) with the rate constants of charge separation (k(CS)) in the range of (1-9) x 10(9) s(-1). A nanosecond transient absorption technique confirmed the electron transfer products, MP center dot+(alkyl)(4)/SWCNT center dot- and/or MP center dot-(alkyl)(4)/SWCNT center dot+ for the two-layer nanohybrids. Upon further coordination of C(60)Im to ZnP, acceleration of charge separation via (ZnP)-Zn-1* in C(60)Im -> ZnP(alkyl)(4)/SWCNT is observed to form C(60)(center dot-)Im -> ZnP center dot+(alkyl)(4)/SWCNT and C(60)(center dot-)Im -> ZnP(alkyl)(4)/SWCNT center dot+ charge separated states as supported by the transient absorption spectra. These characteristic absorptions decay with rate constants due to charge recombination (k(CR)) in the range of (6-10) x 10(6) s(-1), corresponding to the lifetimes of the radical ion-pairs of 100-170 ns. The electro! n transfer in the nanohybrids has further been utilized for light-to-electricity conversion by the construction of proof-of-concept photoelectrochemical solar cells.
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Royal Society of Chemistry
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Physical Chemistry Chemical Physics
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1463-9076
1463-9084
1463-9084