Effects of Ligand Substitution on the Optical and Electrochemical Properties of (Pyridinedipyrrolide)zirconium Photosensitizers.

A series of seven bis(pyridinedipyrrolide)zirconium complexes, Zr(R1PDPR2)2, where [R1PDPR2]2- is the doubly deprotonated form of [2,6-bis(5-R1-3-R2-1H-pyrrol-2-yl)pyridine], were prepared and characterized in solution by NMR, UV/vis absorption, and emission spectroscopy and cyclic voltammetry. The molecular structures were determined by single-crystal X-ray crystallography. All complexes exhibit remarkably long emission lifetimes (τ = 190-576 μs) with high quantum efficiencies (ΦPL = 0.10-0.38) upon excitation with visible light in a benzene solution. The substituents on the pyrrolide rings were shown to have significant effects on the photoluminescence and electrochemical properties of these compounds. The R2 substituents (R2 = H, Me, Ph, or C6F5) show only limited effects on the absorption and emission profiles of the complexes but allow systematic tuning of the ground- and excited-state redox potentials over a range of almost 600 mV. The R1 substituents (R1 = H, Me, Ph, or 2,4,6-Me3Ph) influence both the optical and electrochemical properties through electronic effects. Additionally, the R1 substituents have profound consequences for the structural flexibility and overall stability of the compounds. Distortions of the Zr(PDP)2 core from idealized D2d symmetry in the solid state can be traced to the steric profiles of the R1 substituents and correlate with the observed Stokes shifts for each compound. The complex with the smallest ligand system, Zr(HPDPH)2, coordinates two additional solvent molecules in a tetrahydrofuran (THF) solution, which allowed the isolation of photoluminescent, eight-coordinate Zr(HPDPH)2(THF)2. The photoredox catalytic dehalogenation of aryl iodides and aryl chlorides using the most reducing derivative, Zr(MePDPMe)2, highlights the potential of Zr(PDP)2 photosensitizers to promote challenging reductive transformations under mild conditions upon excitation with green light.