Phenazine as a three-in-one synthon in macrocyclic and coordination framework materials: From discrete macrocycles to adaptive supramolecular systems

This is the authors' abstract. We don't add key points for this paper.

The functional development of macrocycles is no longer limited only by cavity size or binding selectivity; it is increasingly constrained by the small number of building blocks that can simultaneously provide a defined geometry, electronic communication, and chemically addressable sites. Phenazine, a rigid N-heteroarene with tunable redox behavior and accessible coordination/derivatization positions, can integrate these requirements in appropriately designed systems. In this review, the term “three-in-one” is used as a context-dependent design description, rather than a universal performance claim, to denote the co-localization of structural, redox, and interaction/coordination functions. This review summarizes phenazine-based macrocyclic and framework materials across discrete macrocycles, cycloparaphenylenes, covalent organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), metal-organic frameworks (MOFs), and coordination cages. Particular attention is paid to how the phenazine core controls cavity geometry, ligand conformation, metal-ligand communication, charge transfer, and guest binding. The functional discussion is organized around supramolecular recognition, selective capture, heterogeneous catalysis, and electrochemical properties. By connecting molecular macrocycles with extended and coordination-driven frameworks, this review highlights phenazine not simply as another heteroaromatic spacer, but as a redox-active and coordination-capable building block for adaptive supramolecular materials.