title: Fused porphyrin-single-walled carbon nanotube hybrids: efficient formation and photophysical characterization.
abstract: A systematic study of the interaction between π-extended porphyrins and single-walled carbon nanotubes (SWNTs) is reported here. Zinc porphyrins with 1-pyrenyl groups in the 5,15-meso positions, 1, as well as compounds where one or both of the pyrene groups have been fused at the meso and β positions of the porphyrin core, 2 and 3, respectively, have been examined. The strongest binding to SWNTs is observed for porphyrin 3, leading to debundling of the nanotubes and formation of stable suspensions of 3-SWNT hybrids in a range of common organic solvents. Absorption spectra of 3-SWNT suspensions are broad and continuous (λ=400-1400 nm), and the Q-band of 3 displays a significant bathochromic shift of 33 nm. The surface coverage of the SWNTs in the nanohybrids was estimated by spectroscopic and analytical methods and found to reach 64% for (7,6) nanotubes. The size and shape of π-conjugated porphyrins were found to be important factors in determining the strength of the π-π interactions, as the linear anti-3 isomer displays more than 90% binding selectivity compared to the bent syn-3 isomer. Steady-state photoluminescence measurements show quenching of porphyrin emission from the nanohybrids. Femtosecond transient absorption spectroscopy reveals that this quenching results from ultrafast electron transfer from the photoexcited porphyrin to the SWNT (1/kCT=260 fs) followed by rapid charge recombination on a picosecond time scale. Overall, our data demonstrate that direct π-π interaction between fused porphyrins and SWNTs leads to electronically coupled stable nanohybrids.
authors.affiliation: Department of Chemistry, University of Southern California, Los Angeles, California 90089, United States.
authors.forename: Qiwen
authors.initials: Q
authors.lastname: Zhong
authors.forename: Vyacheslav V
authors.initials: VV
authors.lastname: Diev
authors.forename: Sean T
authors.initials: ST
authors.lastname: Roberts
authors.forename: Priscilla D
authors.initials: PD
authors.lastname: Antunez
authors.forename: Richard L
authors.initials: RL
authors.lastname: Brutchey
authors.forename: Stephen E
authors.initials: SE
authors.lastname: Bradforth
authors.forename: Mark E
authors.initials: ME
authors.lastname: Thompson
mesh_terms: D000327:Adsorption; D003460:Crystallization / Q000379:methods*; D004553:Electric Conductivity; D046911:Macromolecular Substances / Q000737:chemistry; D008422:Materials Testing; D008968:Molecular Conformation; D037742:Nanotubes, Carbon / Q000737:chemistry* / Q000648:ultrastructure*; D010316:Particle Size; D011166:Porphyrins / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D046911:Macromolecular Substances; D037742:Nanotubes, Carbon; D011166:Porphyrins