Implementation of redox gradients in hydrogen bonded complexes containing N,N-dimethylaniline, flavin and fullerene derivatives
Implementation of redox gradients in hydrogen bonded complexes containing N,N-dimethylaniline, flavin and fullerene derivatives
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DOI：
10.1039/b918462g
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发表时间：
2010-02
影响因子：
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通讯作者：
M. Murakami;K. Ohkubo;Taku Hasobe;Vito Sgobba;D. Guldi;Florian Wessendorf;A. Hirsch;S. Fukuzumi
中科院分区：
文献类型：
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作者：
M. Murakami;K. Ohkubo;Taku Hasobe;Vito Sgobba;D. Guldi;Florian Wessendorf;A. Hirsch;S. Fukuzumi
通过将电子给体取代的黄素二联体（10-[4′-（N，N-二甲氨基）苯基]异咯嗪：DMA-F1）与一类含有单、双氢键受体的富勒烯衍生物（SRC 60和DRC 60）缔合，形成了多种超分子复合物。通过在470 nm处与DMA-Fl相关的吸收变化的Job图分析来检查相应络合物（即，DMA-Fl和SRC 60或DRC 60）的化学计量。为此，分别确定了DMA-F1-SRC 60和（DMA-F1）2-DRC 60的1：1和1：2络合物化学计量。通过快速注射法形成了非常稳定的团簇形式的分子聚集体。对这些簇的洞察来自透射电子显微镜（TEM）测量，其揭示了直径在200和500 nm之间的范围内的（DMA-Fl-SRC 60）n的网络构型，而对于[（DMA-Fl）2-DRC 60]n可辨别出直径约40 nm的均匀纳米颗粒。通过电泳沉积技术将高度着色的复合团簇组装到覆盖有纳米结构SnO 2膜的光学透明电极上。重要的是光电流作用光谱提供最大IPCE值，其对于[（DMA-F1）2-DRC 60]n是对于（DMA-F1-SRC 60）n的两倍高。为了补充这些研究，通过飞秒激光闪光光解研究了超分子团簇中的电子转移动力学（即，（DMA-F1-SRC60）n和[（DMA-F1）2-DRC60]n）。事实上，我们第一次能够证明从末端电子供体（N，N-二甲基苯胺）部分到末端电子受体（富勒烯）部分的单向电子转移。
A variety of supramolecular complexes were formed by associating an electron donor-substituted flavin dyad (10-[4′-(N,N-dimethylamino)phenyl]isoalloxazine: DMA–Fl) and a family of fullerene derivatives that contain single and double hydrogen bond receptors (SRC60 and DRC60). The stoichiometry of the corresponding complexes, that is, DMA–Fl and SRC60 or DRC60, were examined by Job's plot analysis of the absorption changes linked to DMA–Fl at 470 nm. To this end, 1 : 1 and 1 : 2 complex stoichiometries were determined for DMA–Fl-SRC60 and (DMA–Fl)2-DRC60, respectively. Molecular aggregates in the form of remarkably stable clusters were formed by the fast injection method. Insights into these clusters came from transmission electron microscopy (TEM) measurements, which revealed network configurations for (DMA–Fl-SRC60)n with diameters in the range between 200 and 500 nm, while uniform nanoparticles of about 40 nm diameter were discernible for [(DMA–Fl)2-DRC60]n. The highly colored composite clusters were assembled onto an optically transparent electrode covered with nanostructured SnO2 films by the electrophoretic deposition technique. Important are the photocurrent action spectra providing maximum IPCE values that are twice as high for [(DMA–Fl)2-DRC60]n than for (DMA–Fl-SRC60)n. To complement these studies the dynamics of electron transfer were investigated by femtosecond laser flash photolysis in the supramolecular clusters (i.e., (DMA–Fl-SRC60)n and [(DMA–Fl)2-DRC60]n). As a matter of fact, for the first time we were able to demonstrate the unidirectional electron transfer from the terminal electron donor (N,N-dimethylaniline) moiety to the terminal electron acceptor (fullerene) moiety.