Porphyrin and their versatile metal complexes represent a special class of coordination compounds possessing unique physical-chemical properties. The achievements in the development of the synthetic approaches for the modification of the porphyrin macrocycle allowed the preparation of a variety of functional derivatives for diverse applications. Among a broad diversity of synthetically available metalloporphyrins meso-substituted tetrapyrroles are comprehensively investigated. However, β-substituted porphyrins could be considered as the most suitable models for mimicking the key roles of naturally occurring dyes in vital processes. The introduction of various substituents to the β-positions of the macrocycle opens an access to the tuning of the electronic and, in turn, physical-chemical properties of the obtained complexes. The present review summarizes the synthetic aspects of β-functionalized tetrapyrrolic compounds – heterocycle-appended porphyrins – and their physical-chemical properties. The observed synthetic methodologies are divided onto several parts depending on the type of heterocycle appended to the porphyrin β,β′-positions. The first five parts of the synthetic aspects chapter are devoted to the methods of the annulation of nitrogen-containing heterocycles. Strategies for the preparation of porphyrins bearing annulated sulfur-heterocycles are observed separately. A concluding chapter of the review comprises the most interesting and promising physical-chemical properties of these compounds and related challenges of their practical applications in different fields.

卟啉及其多功能金属配合物代表一类特殊的配位化合物，具有独特的物理化学性质。在开发用于修饰卟啉大环的合成方法方面的成就使得可以制备用于各种应用的多种功能性衍生物。在种类繁多的合成金属卟啉中观异构体中对取代的四吡咯进行了全面的研究。然而，β-取代的卟啉可以被认为是模仿天然染料在生命过程中的关键作用的最合适的模型。将各种取代基引入大环的β-位置，为调节所获得的配合物的电子性质以及物理化学性质提供了途径。本综述总结了β-官能化的四吡咯化合物（杂环附加的卟啉）的合成方面及其理化性质。所观察到的合成方法根据附在卟啉β，β'-位置上的杂环的类型分为几个部分。合成方面一章的前五个部分专门介绍了含氮杂环的环化方法。分别观察到了带有环状硫杂环的卟啉的制备策略。综述的最后一章包括这些化合物最有趣和最有希望的物理化学性质，以及它们在不同领域中的实际应用相关的挑战。