Photoconductivity of Porphyrin Nanochannels Composed of Diprotonated Porphyrin Dications with Saddle Distortion and Electron Donors
Photoconductivity of Porphyrin Nanochannels Composed of Diprotonated Porphyrin Dications with Saddle Distortion and Electron Donors
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DOI：
10.1021/cm802460t
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发表时间：
2008-11
影响因子：
8.6
通讯作者：
Tatsuaki Nakanishi;Takahiko Kojima;K. Ohkubo;Taku Hasobe;K. Nakayama;S. Fukuzumi
中科院分区：
文献类型：
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作者：
Tatsuaki Nakanishi;Takahiko Kojima;K. Ohkubo;Taku Hasobe;K. Nakayama;S. Fukuzumi
以十二苯基卟啉（[H4DPP]Cl2）盐酸盐为原料，通过分子间π−π相互作用自组装制备了以四噻吩烯（TTF）和对氨基酚为内空间给电子客体的超分子结构卟啉纳米通道（pnc）。用x射线晶体学测定了含TTF的PNC （PNC - TTF）的晶体结构。卟啉外围苯基之间存在π−π相互作用，主要沿晶体c轴方向形成柱状结构。在PNC中，通过[H4DPP]Cl2的光激发单重态，客体分子的光诱导电子转移到[H4DPP]Cl2中，客体分子的阳离子自由基和单电子还原的[H4DPP]Cl2 {[H4DPP+•]Cl2}−发生了电子转移。用固体飞秒激光闪光光解和ESR测量对反应进行了检测，以确定电子转移和电动力学的速率常数。
Supramolecular architecture named as porphyrin nanochannels (PNCs), including tetrathiafulvalene (TTF) and p-aminophenol as electron-donating guests in the inner space, was prepared with the hydrochloride salt of dodecaphenylporphyrin ([H4DPP]Cl2) by self-assembly based on intermolecular π−π interactions. The crystal structure of the TTF-included PNC (PNC−TTF) was determined by X-ray crystallography. Intermolecular π−π interaction was recognized among peripheral phenyl groups of the porphyrin, mainly in the direction of the crystallographic c axis to form a column structure. Photoinduced electron transfer from the guest molecules to [H4DPP]Cl2 occurred to give the electron-transfer state involving cation radicals of the guest molecules and one-electron reduced [H4DPP]Cl2, {[H4DPP+•]Cl2}−, via the photoexcited singlet state of [H4DPP]Cl2 in PNC. The reactions were examined by solid-state femtosecond laser flash photolysis and ESR measurements to determine the rate constants of electron transfer and electro...