Biopyrrin Pigments: From Heme Metabolites to Redox-Active Ligands and Luminescent Radicals

ConspectusRedox-active ligands in coordination chemistry not only modulate the reactivity of the bound metal center but also serve as electron reservoirs to store redox equivalents. Among many applications in contemporary chemistry, the scope of redox-active ligands in biology is exemplified by the porphyrin radicals in the catalytic cycles of multiple heme enzymes (e.g., cytochrome P450, catalase) and the chlorophyll radicals in photosynthetic systems. This Account reviews the discovery of two redox-active ligands inspired by oligopyrrolic fragments found in biological settings as products of heme metabolism.Linear oligopyrroles, in which pyrrole heterocycles are linked by methylene or methine bridges, are ubiquitous in nature as part of the complex, multistep biosynthesis and degradation of hemes and chlorophylls. Bile pigments, such as biliverdin and bilirubin, are common and well-studied tetrapyrroles with characteristic pyrrolin-2-one rings at both terminal positions. The coordination chemistry of these open-chain pigments is less developed than that of porphyrins and other macrocyclic oligopyrroles; nevertheless, complexes of biliverdin and its synthetic analogs have been reported, along with fluorescent zinc complexes of phytobilins employed as bioanalytical tools. Notably, linear conjugated tetrapyrroles inherit from porphyrins the ability to stabilize unpaired electrons within their π system. The isolated complexes, however, present helical structures and generally limited stability.Smaller biopyrrins, which feature three or two pyrrole rings and the characteristic oxidized termini, have been known for several decades following their initial isolation as urinary pigments and heme metabolites. Although their coordination chemistry has remained largely unexplored, these compounds are structurally similar to the well-established tripyrrin and dipyrrin ligands employed in a broad variety of metal complexes. In this context, our study of the coordination chemistry of tripyrrin-1,14-dione and dipyrrin-1,9-dione was motivated by the potential to retain on these compact, versatile platforms the reversible ligand-based redox chemistry of larger tetrapyrrolic systems.The tripyrrindione ligand coordinates several divalent transition metals (i.e., Pd(II), Ni(II) Cu(II), Zn(II)) to form neutral complexes in which an unpaired electron is delocalized over the conjugated π system. These compounds, which are stable at room temperature and exposed to air, undergo reversible one-electron processes to access different redox states of the ligand system without affecting the oxidation state and coordination geometry of the metal center. We also characterized ligand-based radicals on the dipyrrindione platform in both homoleptic and heteroleptic complexes. In addition, this study documented noncovalent interactions (e.g., interligand hydrogen bonds with the pyrrolinone carbonyls, π-stacking of ligand-centered radicals) as important aspects of this coordination chemistry. Furthermore, the fluorescence of the zinc-bound tripyrrindione radical and the redox-switchable emission of a dipyrrindione BODIPY-type fluorophore showcased the potential interplay of redox chemistry and luminescence in these compounds. Supported by computational analyses, the portfolio of properties revealed by this investigation takes the tripyrrindione and dipyrrindione motifs of heme metabolites to the field of redox-active ligands, where they are positioned to offer new opportunities for catalysis, sensing, supramolecular systems, and functional materials.