Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 120-749, Korea.
Phys Chem Chem Phys. 2011 Sep 28;13(36):16175-81. doi: 10.1039/c1cp21737b. Epub 2011 Aug 11.
A series of meso-meso, β-β, β-β triply linked linear, radial and square-type zinc(II) porphyrin arrays consist of the constituent porphyrin units and naphthalene junctions. To understand the unique nature of triply linked porphyrin arrays, numerous research activities have been focused on the electronic structures of the constituent porphyrin units. In this study, however, we have paid attention to the role of the naphthalene junction in the electronic delocalization of various triply linked porphyrin arrays. On the basis of our study, we have unveiled that unique π-conjugation behaviors in triply linked porphyrin arrays are induced by their intrinsic molecular orbital interactions and subsequently by antiaromatic junctions. Furthermore, the structural deformation by triple linkages gives rise to a deteriorative effect on the electronic delocalization between inner and outer porphyrin units. Finally, we propose a different type of electron delocalization in linear multichromophoric systems by alternating aromatic and antiaromatic units.
一系列介孔-介孔、β-β、β-β 三重连接的线性、径向和正方形型锌（II）卟啉阵列由组成卟啉单元和萘连接体组成。为了了解三重连接卟啉阵列的独特性质，已经进行了大量的研究活动来关注组成卟啉单元的电子结构。然而，在本研究中，我们关注了萘连接体在各种三重连接卟啉阵列的电子离域中的作用。在此基础上，我们揭示了三重连接卟啉阵列中的独特π-共轭行为是由其内在的分子轨道相互作用以及随后的反芳香性连接体诱导的。此外，三重键的结构变形导致了内部和外部卟啉单元之间的电子离域的恶化。最后，我们通过交替的芳香族和反芳香族单元提出了一种在线性多生色团体系中电子离域的不同类型。
