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
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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DOI：
10.1021/cm062031k
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发表时间：
2007-01-09
影响因子：
8.6
通讯作者：
Fukuzumi, Shunichi
中科院分区：
文献类型：
--
作者：
Kojima, Takahiko;Harada, Ryosuke;Fukuzumi, Shunichi
鞍形变形的钼(V)-十二苯基卟啉 (H2DPP) 络合物 [Mo(DPP)(O)(OMe)] (1) 在通过甲醇蒸汽扩散从甲苯中重结晶的过程中转化为 [Mo(DPP)(O)(H2O)](+) (2)。配合物2通过自组装形成直径为1 nm的卟啉纳米管，同时在纳米管中选择性包含三种新型四核Mo(VI)-氧簇。这种卟啉纳米管表现出两亲特性，即疏水性卟啉表面和由水配体制成的亲水性内球，包括离子和亲水实体。每个纳米管之间没有直接的相互作用；然而，结晶的甲苯分子通过分子间 pi-pi 和 CH/pi 相互作用将纳米管连接在一起。透射电子显微镜测量和能量色散X射线分析表明，卟啉纳米管的直径可以通过所包含的Mo-oxo簇的尺寸来改变，并且可以获得卟啉纳米环。这些结果表明，使用 DPP 配合物通过协同模板辅助自组装可以制备多种卟啉纳米管结构。
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 pi-pi and CH/pi 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.