Zhang Yuehong, Oh Juwon, Wang Kang, Chen Chao, Cao Wei, Park Kyu Hyung, Kim Dongho, Jiang Jianzhuang
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing, 100083, P.R. China.
Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749, Korea.
Chemistry. 2016 Mar 18;22(13):4492-9. doi: 10.1002/chem.201504837. Epub 2016 Feb 16.
Phthalocyanine (Pc) and porphyrin (Por) chromophores have been fused through the benzo[α]pyrazine moiety, resulting in unprecedented heteroleptic tetrapyrrole-fused dimers and trimers. The heteroleptic tetrapyrrole nature has been clearly revealed based on single-crystal X-ray diffraction analysis of the zinc dimer. Electrochemical analysis, theoretical calculations, and time-resolved spectroscopic results disclose that the two/three-tetrapyrrole-fused skeletons behave as one totally π-conjugated system as a result of the strong conjugative interaction between/among the tetrapyrrole chromophores. In particular, the effectively extended π-electron system through the fused-bridge induced strong electronic communication between the Pc and Por moieties and large transition dipole moments in the Pc-Por-fused systems, providing high fluorescence quantum yields (>0.13) and relatively long excited state lifetimes (>1.3 ns) in comparison with their homo-tetrapyrrole-fused analogues.
酞菁（Pc）和卟啉（Por）发色团已通过苯并[α]吡嗪部分融合，形成了前所未有的杂配四吡咯融合二聚体和三聚体。基于锌二聚体的单晶X射线衍射分析，杂配四吡咯的性质已得到明确揭示。电化学分析、理论计算和时间分辨光谱结果表明，由于四吡咯发色团之间的强共轭相互作用，两个/三个四吡咯融合骨架表现为一个完全π共轭体系。特别是，通过融合桥有效扩展的π电子体系在Pc - Por融合体系中诱导了Pc和Por部分之间的强电子通信以及大的跃迁偶极矩，与它们的同配四吡咯融合类似物相比，提供了高荧光量子产率（>0.13）和相对较长的激发态寿命（>1.3 ns）。
