Unexpected Boost in Activity of a Cu(I) Photosensitizer by Stabilizing a Transient Excited State

In this study, we present a slight but surprisingly successful structural modification of the previously reported heteroleptic Cu(I) photosensitizer Cubiipo ([(xantphos)Cu(biipo)]PF₆; biipo = 16H-benzo-[4',5']-isoquinolino-[2',1':1,2]-imidazo-[4,5-f]-[1,10]-phenanthrolin-16-one). As a key feature, biipo bears a naphthalimide unit at the back, which is directly fused to a phenanthroline moiety to extend the conjugated π-system. This ligand was now altered to include two additional methyl groups at the 2,9-positions at the phenanthroline scaffold. Comparing the novel Cudmbiipo complex to its predecessor, ultrafast transient absorption spectroscopy reveals the efficient suppression of a major deactivation pathway by stabilization of a transient triplet state. Furthermore, quantitative measurements of singlet oxygen evolution in solution confirmed that a larger fraction of the excited-state population is transferred to the photocatalytically active ligand-centered triplet ³LC state with a much longer lifetime of ∼30 μs compared to Cubiipo (2.6 μs). In addition, Cudmbiipo was compared with the well-established reference complex Cubcp ([(xantphos)Cu(bathocuproine)]PF₆) in terms of its photophysical and photocatalytic properties by applying time-resolved femto- and nanosecond absorption, step-scan Fourier transform infrared (FTIR), and emission spectroscopies. Superior light-harvesting properties and a greatly enhanced excited-state lifetime with respect to Cubcp enable Cudmbiipo to be more active in exemplary photocatalytic applications, i.e., in the formation of singlet oxygen and the isomerization of (E)-stilbene.