In this study, we present a slight but surprisingly successful structural modification of the previously reported heteroleptic Cu(I) photosensitizer ([(xantphos)Cu(biipo)]PF; = 16-benzo-[4',5']-isoquinolino-[2',1':1,2]-imidazo-[4,5-]-[1,10]-phenanthrolin-16-one). As a key feature, 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 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 LC state with a much longer lifetime of ∼30 μs compared to (2.6 μs). In addition, was compared with the well-established reference complex ([(xantphos)Cu(bathocuproine)]PF) 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 enable to be more active in exemplary photocatalytic applications, ., in the formation of singlet oxygen and the isomerization of ()-stilbene.

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http://dx.doi.org/10.1021/acs.inorgchem.2c01468DOI Listing

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