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Updated: Jun 21, 2026

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Three-coordinate, phosphine-ligated azadipyrromethene complexes of univalent group 11 metals
Thomas S Teets1, James B Updegraff, Arthur J Esswein
1Department of Chemistry, Case Western Reserve University, Cleveland, Ohio 44106, USA.
Abstract:
Tetraarylazadipyrromethenes are Lewis basic, red-light absorbing dyes with optical properties conducive to sensing and therapeutic applications. Recently, transition metal complexes of these ligands have been described. Here, we report a series of three-coordinate Group 11 complexes of unsubstituted and methoxy-substituted tetraarylazadipyrromethenes. In each, two pyrrole nitrogens chelate a d(10) metal ion; triphenyl- or triethylphosphine occupies a third coordination site. New complexes are characterized by multinuclear NMR, X-ray crystallography, optical absorption and emission spectroscopy, and elemental analysis. Solid-state structures show trigonal planar geometries about the metal centers, and reveal pervasive intra- and intermolecular pi-stacking interactions. Visible light absorption intensifies with metal binding, in some cases shifting to longer wavelengths. The complexes weakly luminesce in the red region; emission wavelengths and quantum yields are similar to those of free azadipyrromethenes. Methoxy-substitution on the ligand red-shifts optical features, whereas substitution of triethylphosphine for triphenylphosphine in the third coordination site has minimal structural or spectral consequences.
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