Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, India.
Department of Chemistry, BMS College of Engineering , Bull Temple Road, Bengaluru 560019, India.
Chem Rev. 2017 Feb 22;117(4):3254-3328. doi: 10.1021/acs.chemrev.6b00496. Epub 2016 Nov 4.
The heteroatom-containing porphyrin analogues or core-modified porphyrins that resulted from the replacement of one or two pyrrole rings with other five-membered heterocycles such as furan, thiophene, selenophene, tellurophene, indene, phosphole, and silole are highly promising macrocycles and exhibit quite different physicochemical properties compared to regular azaporphyrins. The properties of heteroporphyrins depend on the nature and number of different heterocycle(s) present in place of pyrrole ring(s). The heteroporphyrins provide unique and unprecedented coordination environments for metals. Unlike regular porphyrins, the monoheteroporphyrins are known to stabilize metals in unusual oxidation states such as Cu and Ni in +1 oxidation states. The diheteroporphyrins, which are neutral macrocycles without ionizable protons, also showed interesting coordination chemistry. Thus, significant progress has been made in last few decades on core-modified porphyrins in terms of their synthesis, their use in building multiporphyrin arrays for light-harvesting applications, their use as ligands to form interesting metal complexes, and also their use for several other studies. The synthetic methods available in the literature allow one to prepare mono- and diheteroporphyrins and their functionalized derivatives, which were used extensively to prepare several covalent and noncovalent heteroporphyrin-based multiporphyrin arrays. The methods are also developed to synthesize different hetero analogues of porphyrin derivatives such as heterocorroles, heterochlorins, heterocarbaporphyrinoids, heteroatom-substituted confused porphyrins, and so on. This Review summarizes the key developments that have occurred in heteroporphyrin chemistry over the last four decades.
含有杂原子的卟啉类似物或核心修饰卟啉是通过用呋喃、噻吩、硒吩、碲吩、茚、磷杂环戊二烯和硅杂环戊二烯等五元杂环替代一个或两个吡咯环而得到的，它们是很有前途的大环，与常规的氮杂卟啉相比，表现出截然不同的物理化学性质。杂卟啉的性质取决于取代吡咯环的不同杂环的性质和数量。杂卟啉为金属提供了独特的、前所未有的配位环境。与常规卟啉不同，单杂卟啉已知可以稳定金属处于不寻常的氧化态，如 Cu 和 Ni 的+1 氧化态。二杂卟啉是中性大环，没有可电离的质子，也表现出有趣的配位化学。因此，在过去几十年中，在核心修饰卟啉方面取得了重大进展，包括它们的合成、在用于光捕获应用的多卟啉阵列中的应用、作为配体形成有趣的金属配合物的应用，以及用于其他一些研究的应用。文献中提供的合成方法允许人们制备单杂和二杂卟啉及其功能化衍生物，这些衍生物被广泛用于制备几种共价和非共价杂卟啉基多卟啉阵列。还开发了方法来合成不同的杂原子卟啉衍生物的类似物，如杂金属叶啉、杂氯叶啉、杂碳杂卟啉、杂原子取代的混淆卟啉等。本综述总结了过去四十年中杂卟啉化学的关键发展。
