Institute of Organic Chemistry Polish Academy of Sciences, Kasprzaka 44/52 01-224, Warsaw, Poland.
Chem Commun (Camb). 2012 Oct 18;48(81):10069-86. doi: 10.1039/c2cc31279d.
Porphyrins fused with other aromatic units at the meso- and β-positions have recently emerged as a hot topic of research. Their synthesis typically starts with preparation of precursors via either Suzuki coupling of a meso-bromoporphyrin or mixed-aldehyde condensation, and is followed by oxidative aromatic coupling, often using high-valent metal reagents (DDQ/Sc(OTf)(3) and Fe(III) salts are among the most popular). In recent years, porphyrins were oxidatively coupled not only with well-known aromatic hydrocarbons such as naphthalene and pyrene, but also with more complex heterocyclic fragments, including indole, phenanthro[1,10,9,8-cdefg]carbazole and BODIPY. A subtle relationship exists between the output of intramolecular oxidative coupling and the nature of the second aromatic moiety, cation in the porphyrin cavity, oxidant, and type of remaining meso-substituent. The extension of the porphyrin chromophore leads to significant change in linear and non-linear optical properties. Very strong bathochromic shifts of absorption (λ(max) reaching 1.5-2 microns in some cases) and increases in two-photon absorption cross-sections are typical for these functional dyes.
具有中-和 β-位稠合的芳环单元的卟啉最近成为研究的热点。它们的合成通常从通过 Suzuki 偶联中-溴代卟啉或混合醛缩合来制备前体开始，然后进行氧化芳构化偶联，通常使用高价金属试剂（DDQ/Sc(OTf)(3)和 Fe(III)盐是最受欢迎的试剂之一）。近年来，卟啉不仅与萘和芘等众所周知的芳烃，而且与更复杂的杂环片段（包括吲哚、菲咯嗪[1,10,9,8-cdefg]咔唑和 BODIPY）发生了氧化偶联。分子内氧化偶联的产物与第二个芳环部分的性质、卟啉腔中的阳离子、氧化剂和剩余的中取代基的类型之间存在微妙的关系。卟啉发色团的扩展导致线性和非线性光学性质发生显著变化。这些功能染料的典型特征是吸收的明显红移（在某些情况下 λ(max) 达到 1.5-2 微米）和双光子吸收截面的增加。
