Akasaka Takeshi, Nakata Akira, Rudolf Marc, Wang Wei-Wei, Yamada Michio, Suzuki Mitsuaki, Maeda Yutaka, Aoyama Ryo, Tsuchiya Takahiro, Nagase Shigeru, Guldi Dirk M
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8577, Japan.
Foundation for Advancement of International Science, Ibaraki, 305-0821, Japan.
Chempluschem. 2017 Jul;82(7):1067-1072. doi: 10.1002/cplu.201600391. Epub 2016 Sep 21.
A newly designed electron donor-acceptor conjugate consisting of an endohedral dimetallofullerene (La @I -C ) and phenoxazine (POZ) was successfully synthesized under Prato conditions. Our results document that the 1,3-dipolar cycloaddition took place across the [5,6] junction to afford exclusively the corresponding [5,6] cycloadduct. The structure of the conjugate was characterized by means of NMR spectroscopy, absorption spectroscopy, and electrochemical studies. Computational calculations suggest that the electron density of the highest occupied molecular orbital (HOMO) is distributed on the POZ moiety, whereas that of the lowest unoccupied molecular orbital (LUMO) is located at the endohedral La atoms, leading to efficient separation of the HOMO and LUMO in the conjugate. Time-resolved absorption spectroscopic investigations and spectroelectrochemical measurements corroborate the formation of the energetically low-lying (La @I -C ) -(POZ) radical-ion-pair state by means of ultrafast through-space electron transfer.
在普拉托条件下成功合成了一种新设计的由内嵌双金属富勒烯（La@I-C）和吩恶嗪（POZ）组成的电子供体-受体共轭物。我们的结果表明，1,3-偶极环加成反应发生在[5,6]连接处，仅生成相应的[5,6]环加成产物。通过核磁共振光谱、吸收光谱和电化学研究对该共轭物的结构进行了表征。计算计算表明，最高占据分子轨道（HOMO）的电子密度分布在POZ部分，而最低未占据分子轨道（LUMO）的电子密度位于内嵌的La原子处，导致共轭物中HOMO和LUMO有效分离。时间分辨吸收光谱研究和光谱电化学测量通过超快的空间电子转移证实了能量较低的（La@I-C）-（POZ）自由基离子对态的形成。
