Jana Atanu, Gobeze Habtom B, Ishida Masatoshi, Mori Toshiyuki, Ariga Katsuhiko, Hill Jonathan P, D'Souza Francis
Supermolecules Group, WPI Center for Materials Nanoarchitectonics, National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, Ibaraki 3050044, Japan.
Dalton Trans. 2015 Jan 7;44(1):359-67. doi: 10.1039/c4dt03157a.
A novel electron rich, tetrathiafulvalene fused zinc porphyrin, (TTF)4PZn, has been newly synthesized and characterized using spectral and electrochemical methods. In spite of the presence of eight t-butyl groups, (TTF)4PZn exhibited appreciable aggregation in solution. Scanning electron microscopic (SEM) imaging of the aggregates revealed their spherical particulate morphology. Attenuation of intermolecular aggregation was possible by metal-ligand coordination of a nitrogenous ligand. Further, using this strategy, a donor-acceptor hybrid was formed by coordinating imidazole functionalized fullerene as an electron acceptor. The occurrence of intrasupramolecular ultrafast photoinduced charge separation has been established using fluorescence and transient absorption spectroscopic techniques. The determined rate of charge separation, kCS, and rate of charge recombination, kCR were found to be 1.4 × 10(11) s(-1) and 2.5 × 10(6) s(-1), respectively. The lower kCR values indicate charge stabilization in the assembled donor-acceptor conjugate via an electron transfer-hole transfer mechanism.
一种新型富电子的、四硫富瓦烯稠合锌卟啉（TTF）4PZn已被新合成，并采用光谱和电化学方法进行了表征。尽管存在八个叔丁基，（TTF）4PZn在溶液中仍表现出明显的聚集现象。对聚集体的扫描电子显微镜（SEM）成像显示出它们的球形颗粒形态。通过含氮配体的金属-配体配位可以减弱分子间聚集。此外，利用该策略，通过配位咪唑功能化的富勒烯作为电子受体形成了供体-受体杂化物。利用荧光和瞬态吸收光谱技术确定了分子内超快光诱导电荷分离的发生。电荷分离速率kCS和电荷复合速率kCR分别为1.4×10(11) s(-1)和2.5×10(6) s(-1)。较低的kCR值表明通过电子转移-空穴转移机制，组装的供体-受体共轭物中的电荷得到了稳定。
