Enhancing the Visible-Light Absorption and Excited-State Properties of Cu(I) MLCT Excited States

A computationally inspired Cu(I) metal-to-ligand charge transfer (MLCT) chromophore, [Cu(sbmpep) 2 ] + (sbmpep = 2,9-di( sec -butyl)-3,8-dimethyl-4,7-di(phenylethynyl)-1,10-phenanthroline), was synthesized in seven total steps, prepared from either dichloro- or dibromophenanthroline precursors. Complete synthesis, structural characterization, and electrochemistry, in addition to static and dynamic photophysical properties of [Cu(sbmpep) 2 ] +, are reported on all relevant time scales. UV–Vis absorption spectroscopy revealed significant increases in oscillator strength along with a concomitant bathochromic shift in the MLCT absorption bands with respect to structurally related model complexes (ε = 16 500 M –1 cm –1 at 491 nm). Strong red photoluminescence (Φ = 2.7%, λ max = 687 nm) was observed from [Cu(sbmpep) 2 ] +, which featured an average excited-state lifetime of 1.4 μs in deaerated dichloromethane. Cyclic and differential pulse voltammetry revealed ∼300 mV positive shifts in the measured one-electron reversible reduction and oxidation waves in relation to a Cu(I) model complex possessing identical structural elements without the π-conjugated 4,7-substituents. The excited-state redox potential of [Cu(sbmpep) 2 ] + was estimated to be −1.36 V, a notably powerful reductant for driving photoredox chemistry. The combination of conventional and ultrafast transient absorption and luminescence spectroscopy successfully map the excited-state dynamics of [Cu(sbmpep) 2 ] + from initial photoexcitation to the formation of the lowest-energy MLCT excited state and ultimately its relaxation to the ground state. This newly conceived molecule appears poised for photosensitization reactions involving energy and electron-transfer processes relevant to photochemical upconversion, photoredox catalysis, and solar fuels photochemistry.