Department of Chemistry, Graduate School of Science and ‡Research Center for Materials Science, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
J Am Chem Soc. 2014 Apr 30;136(17):6505-9. doi: 10.1021/ja502898t. Epub 2014 Apr 15.
To generate integrated organized molecular properties, multiple molecular components are required to be assembled into the molecular system with sequential and spatial accuracy in accordance with the design of the molecular assembly. Herein, we present a novel programmable synthesis of a cofacially stacked porphyrin array via repetitive construction of a peptide duplex. We designed and synthesized a novel porphyrin having two artificial amino acid moieties at the trans meso-positions. The amino acid moieties can be connected with another porphyrin unit by repetitive doubly coupling reactions to afford the peptide duplex bridged by the porphyrins. In the duplex, the porphyrin units are stacked cofacially, and the efficient electronic communication among the arrayed porphyrin units was characterized by split redox waves in the cyclic voltammograms. We also demonstrated the three different square-planar metal ions, namely Cu(2+), Ni(2+), and Pd(2+), were arranged inside the ladder-type porphyrin array in a programmable fashion.
为了生成集成的有序分子性质，需要将多个分子组件按照分子组装的设计，以顺序和空间精度组装到分子系统中。在此，我们通过重复构建肽二聚体，提出了一种新型的共面堆叠卟啉阵列的可编程合成方法。我们设计并合成了一种新型的卟啉，其在反式间位具有两个人工氨基酸部分。通过重复的双偶联反应，氨基酸部分可以与另一个卟啉单元连接，从而得到由卟啉桥接的肽二聚体。在二聚体中，卟啉单元共面堆叠，并且通过循环伏安法中的分裂氧化还原波来表征排列的卟啉单元之间的有效电子通信。我们还证明了三种不同的平面正方形金属离子，即 Cu(2+)、Ni(2+)和 Pd(2+)，可以以可编程的方式排列在梯形卟啉阵列内。
