Synthesis, Photochemistry, and Electrochemistry of Single-Wall Carbon Nanotubes with Pendent Pyridyl Groups and of Their Metal Complexes with Zinc Porphyrin. Comparison with Pyridyl-Bearing Fullerenes

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• 作者：Mercedes Alvaro ; Pedro Atienzar ; Pilar de la Cruz ; Juan L. Delgado ; Vincent Troiani ; Hermenegildo Garcia ; Fernando Langa ; Amit Palkar ; and Luis Echegoyen
• 刊名：Journal of the American Chemical Society
• 出版年：2006
• 出版时间：May 24, 2006
• 年：2006
• 卷：128
• 期：20
• 页码：6626 - 6635
• 全文大小：457K
• 年卷期：v.128,no.20(May 24, 2006)
• ISSN：1520-5126

文摘

A soluble, functionalized Py-SWNT has been synthesized and characterized by solution ¹H and¹³C NMR, FT-Raman, and electron microscopy. Experimental data indicate that Py-SWNT has short tubeswith pentyl esters at the tips and pyridyl isoxazolino units along the walls. The synthesis of Py-SWNT isbased on a 1,3-dipolar cycloaddition of a nitrile oxide on the SWNT walls, similar to 1,3-dipolar cycloadditionsthat are common for fullerene functionalization. The resulting Py-SWNT forms a complex with a zincporphyrin (ZnPor) in a way similar to that reported for pyridyl-functionalized [60]-fullerenes. Formation ofthis metal-ligand complex was firmly established by a detailed electrochemical study. However, in contrastto the behavior observed for the ZnPor/Py-C₆₀ complex, photochemical excitation of the complex betweenZnPor/Py-SWNT does not lead to electron transfer with the generation of charge-separated states.Fluorescence and laser flash studies indicate that the main process is energy transfer from the singletZnPor excited state to the Py-SWNT with observation of emission from Py-SWNT. Triplet ZnPor excited-state quenching by Py-SWNT is only observed in polar solvents such as DMF, but not in benzonitrile.