Formation, spectral, electrochemical, and photochemical behavior of zinc N-confused porphyrin coordinated to imidazole functionalized fullerene dyads.
Formation, spectral, electrochemical, and photochemical behavior of zinc N-confused porphyrin coordinated to imidazole functionalized fullerene dyads.
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DOI：
10.1021/ic0601687
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发表时间：
2006-05
影响因子：
4.6
通讯作者：
F. D’Souza;Phillip M. Smith;Lisa M. Rogers;M. Zandler;D.M. Shafiqul Islam;Y. Araki;O. Ito
中科院分区：
文献类型：
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作者：
F. D’Souza;Phillip M. Smith;Lisa M. Rogers;M. Zandler;D.M. Shafiqul Islam;Y. Araki;O. Ito
以四苯基锌卟啉的结构异构体锌氮杂卟啉（ZnNCP）为给体，富勒烯为电子受体，构建了给体-受体二联体。两个衍生物，吡啶配位的锌N-混乱卟啉（Py：ZnNCP）和锌N-混乱卟啉二聚体（ZnNCP-二聚体）被用来形成二联体与咪唑附加富勒烯吡咯烷（C60 Im）。这些卟啉异构体通过轴向配位形成了定义明确的1：1超分子二联体（C60 Im：ZnNCP）。通过光学吸收和发射光谱、ESI-mass、1H NMR和电化学方法对其进行了表征。发现C60 Im：ZnNCP的结合常数K为2.8 × 10（4）M（-1）。用密度泛函B3 LYP/3- 21 G方法研究了C60 Im：ZnNCP的几何结构和电子结构。发现HOMO在ZnNCP实体上，而LUMO主要在富勒烯实体上。采用循环伏安法研究了C60 Im：ZnNCP在邻二氯苯、0.1 n-Bu 4 NClO 4溶液中的电化学性能。发现Py：ZnNCP与Py：ZnTPP相比更容易氧化超过340 mV。在通过轴向配位形成二联体后，第一次氧化显示出近90 mV的阳极位移。从单重态激发ZnNCP的光致电荷分离的证据建立从时间分辨的发射和纳秒瞬态吸收研究的附加富勒烯。
Donor-acceptor dyads were constructed using zinc N-confused porphyrin (ZnNCP), a structural isomer of zinc tetraphenylporphyrin, as a donor, and fullerene as an electron acceptor. Two derivatives, pyridine-coordinated zinc N-confused porphyrin (Py:ZnNCP) and the zinc N-confused porphyrin dimer (ZnNCP-dimer) were utilized to form the dyads with an imidazole-appended fulleropyrrolidine (C60Im). These porphyrin isomers formed well-defined 1:1 supramolecular dyads (C60Im:ZnNCP) via axial coordination. The dyads were characterized by optical absorption and emission, ESI-mass, 1H NMR, and electrochemical methods. The binding constant, K, was found to be 2.8 x 10(4) M(-1) for C60Im:ZnNCP. The geometric and electronic structure of C60Im:ZnNCP were probed by using DFT B3LYP/3-21G methods. The HOMO was found to be on the ZnNCP entity, while the LUMO was primarily on the fullerene entity. The electrochemical properties of C60Im:ZnNCP was probed using cyclic voltammetry in o-dichlorobenzene, 0.1 n-Bu4NClO4. The Py:ZnNCP was found to be easier to oxidize by over 340 mV compared to Py:ZnTPP. Upon dyad formation via axial coordination, the first oxidation revealed an anodic shift of nearly 90 mV. Evidence of photoinduced charge separation from the singlet excited ZnNCP to the appended fullerene was established from time-resolved emission and nanosecond transient absorption studies.