The development of artificial porphyrinoids embedded with functional building blocks

Abstract

The synthesis and applications of artificial porphyrinoids containing various functional building blocks by replacement of the pyrrole subunit have been summarized.

Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds: Synthetic Routes, Properties, and Applications

“…In the following discussion, the structures will generally be classified as porphyrinoids if they were considered as such by the original authors. Various aspects of porphyrinoid chemistry, relevant to the present chapter, have been reviewed by several groups. ,− A few more general reviews on heteroaromatic macrocycles have also been published, notably the yearly chapters in Progress in Heterocyclic Chemistry by Newkome (since 1989) and a chapter on heteracyclophanes by Vögtle et al The largest circulene systems, which constitute a small class of macrocycles different from both porphyrinoids and cyclophanes, have been reviewed in section .…”

Surface-Mediated Ring-Opening and Porphyrin Deconstruction via Conformational Distortion

“…The breakdown of such species via the opening of the macrocycle is crucial for various biological processes, such as heme degradation, leaf senescence, and fruit ripening. − A key step is the attack of the macrocycle by oxygenase, inducing the ring-opening and constituting distinct tetrapyrrole catabolites. − Together with the intricate macrocycle-opening reactions that might proceed with or without loss of carbon atoms, , the products are of pivotal relevance. For example, bilirubin, a heme catabolite, can further oxidatively react to form tripyrrins. , Such oligopyrroles likewise attracted attention from a material science perspective, for example, di- and tripyrrins can be employed as metal–complexing agents in functional organometallic compounds , and as fluorescent sensors. , Furthermore, the synthesis of artificial porphyrinoids, with expanded, contracted, or otherwise modified macrocycles, frequently relies on precursors combining one, two, or three pyrrolic units . Interfacial nanoscience has provided manifold insights into surface-supported tetrapyrrole systems and their rich chemistry, , frequently exceeding the scope of typically stability-limited characterization in solution.…”

“…10,11 Furthermore, the synthesis of artificial porphyrinoids, with expanded, contracted, or otherwise modified macrocycles, frequently relies on precursors combining one, two, or three pyrrolic units. 12 Interfacial nanoscience has provided manifold insights into surfacesupported tetrapyrrole systems and their rich chemistry, 13,14 frequently exceeding the scope of typically stability-limited characterization in solution. Nonetheless, synthetic porphyrin catabolites, such as di-or tripyrrins, remained largely elusive on solid supports.…”

Expanding the Porphycene Core: Modification and Metalation

“…[8][9][10] Synthetic efforts aimed at modifying the porphycene core to fine-tune desired properties have focused on incorporating new heterocyclic functionalities, synthesis of species containing diverse β-and vinylic-substitution patterns, and use of so-called functional building blocks. 11,12 Previous reviews have gone into extensive detail regarding the syn-thesis and properties of porphycene-based systems. [13][14][15][16] In an effort to complement this earlier literature, we present here a brief summary of our contributions in elaborating the porphycene core.…”