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Porphyrin Nanotubes Based on Self-Assembly of Mo(V)−Dodecaphenylporphyrin Complexes and Inclusion of Mo−Oxo Clusters:  Synthesis and Characterization by X-ray Crystallography and Transmission Electron Microscopy

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Department of Chemistry, Faculty of Sciences, and The Research Laboratory for High Voltage Electron Microscopy, Kyushu University, Hakozaki, Higashi-Ku, Fukuoka 812-8581, and Department of Material and Life Science, Graduate School of Engineering, Osaka University, SORST, Japan Science and Technology Agency (JST), 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
Cite this: Chem. Mater. 2007, 19, 1, 51–58
Publication Date (Web):November 22, 2006
https://doi.org/10.1021/cm062031k
Copyright © 2007 American Chemical Society
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Abstract

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A saddle-distorted molybdenum(V)−dodecaphenylporphyrin (H2DPP) complex, [Mo(DPP)(O)(OMe)] (1), was converted to [Mo(DPP)(O)(H2O)]+ (2) in the course of recrystallization from toluene with vapor diffusion of methanol. The complex 2 was organized via self-assembly to form a porphyrin nanotube having a diameter of 1 nm, concomitant with size-selective inclusion of three kinds of novel tetranuclear Mo(VI)−oxo clusters in the nanotube. This porphyrin nanotube exhibits amphiphilic characteristics, that is, a hydrophobic porphyrin surface and a hydrophilic inner-sphere made of aquo ligands to include ionic and hydrophilic entities. Each nanotube has no direct interaction; however, the toluene molecules of crystallization linked the nanotubes together with intermolecular π−π and CH/π interactions. Transmission electron microscopy measurements and energy-dispersive X-ray analysis revealed that the diameters of porphyrin nanotubes could be altered by the size of the Mo−oxo clusters included and also a porphyrin nanoring could be obtained. These results indicate that a variety of porphyrin nanotubular structures can be fabricated by using DPP complexes via cooperatively template-assisted self-assembly.

*

 To whom correspondence should be addressed. E-mail:  [email protected] chem.eng.osaka-u.ac.jp.

†

 Department of Chemistry, Kyushu University.

‡

 Present address:  Department of Material and Life Science, Graduate School of Engineering, Osaka University, Japan Science and Technology Agency (JST), 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.

‖

 Present address:  Center for Future Chemistry, Kyushu University, 744 Moto-oka, Fukuoka 819-0395, Japan.

§

 The Research Laboratory for High Voltage Electron Microscopy, Kyushu University.

⊥

 Osaka University.

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Crystallographic data (CIF) for 2, time-course of conductivity of 2, and additional TEM images. This material is available free of charge via the Internet at http://pubs.acs.org.

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