Ru­(II)- and Cu­(I)-based photosensitizers featuring the recently developed biipo ligand (16H-benzo-[4′,5′]-isoquinolino-[2′,1′,:1,2]-imidazo-[4,5-f]-[1,10]-phenanthrolin-16-one) were comprehensively investigated by X-ray crystallography, electrochemistry, and especially several time-resolved spectroscopic methods covering all time scales from femto- to milliseconds. The analysis of the experimental results is supported by density functional theory (DFT) calculations. The biipo ligand consists of a coordinating 1,10-phenanthroline moiety fused with a 1,8-naphthalimide unit, which results in an extended π-system with an incorporated electron acceptor moiety. In a previous study, it was shown that this ligand enabled a Ru­(II) complex that is an efficient singlet oxygen producer and of potential use for other light-driven applications due to its long emission lifetime. The goal of our here presented research is to provide a full spectroscopic picture of the processes that follow optical excitation. Interestingly, the Ru­(II) and Cu­(I) complexes differ in their characteristics even though the lowest electronically excited states involve in both cases the biipo ligand. The combined spectroscopic results indicate that an emissive 3MLCT state and a rather dark 3LC state are populated, each to some extent. For the Cu­(I) complex, most of the excited population ends up in the 3LC state with an extraordinary lifetime of 439 μs in the solid state at 20 K, while a significant population of the 3MLCT state causes luminescence for the Ru­(II) complex. Hence, there is a balance between these two states, which can be tuned by altering the metal center or even by thermal energy, as suggested by the temperature-dependent experiments.

To bind or not to bind: Driven by the motivation to increase the (photo)stability of traditional Cu(I) photosensitizers, multidentate diimine ligands, which contain two additional donor sites, were designed. To this end, a systematic series of four 1,10phenanthroline ligands with either OR or SR (R = i Pr or Ph) donor groups at the 2 and 9 positions and their resulting hetero-and homoleptic Cu(I) complexes were prepared. In addition, the related Ru(II) complexes were also synthesized to study the effect of another metal center. In the following, a combination of NMR spectroscopy and X-ray analysis was used to evaluate the impact of the additional donor moieties on the coordination behavior. Most remarkably, for the homoleptic bis(diimine)copper(I) complexes, a pentacoordinated copper center, corresponding to a (4 + 1)-fold coordination mode, was found in the solid state. This additional binding is the first indication that the extra donor might also occupy a free coordination site in the excited-state complex, modifying the nature of the excited states and their respective deactivation processes. Therefore, the electrochemical and photophysical properties of all novel complexes (in total 13) were studied in detail to assess the potential of these photosensitizers for future applications within solar energy conversion schemes. Finally, the photostabilities and a potential degradation mechanism were analyzed for representative samples.

A systematic series of four novel homo‐ and heteroleptic Cu I photosensitizers based on tetradentate 1,10‐phenanthroline ligands of the type X^N^N^X containing two additional donor moieties in the 2,9‐position (X=SMe or OMe) were designed. Their solid‐state structures were assessed by X‐ray diffraction. Cyclic voltammetry, UV‐vis absorption, emission and X‐ray absorption spectroscopy were then used to determine their electrochemical, photophysical and structural features in solution. Following, time‐resolved X‐ray absorption spectroscopy in the picosecond time scale, coupled with time‐dependent density functional theory calculations, provided in‐depth information on the excited state electron configurations. For the first time, a significant shortening of the Cu−X distance and a change in the coordination mode to a pentacoordinated geometry is shown in the excited states of the two homoleptic complexes. These findings are important with respect to a precise understanding of the excited state structures and a further stabilization of this type of photosensitizers.

The capture and storage of solar energy is a promising option to overcome current energy issues. To put such systems into practice, molecular photosensitizers should be based on abundant metals and possess a strong absorption capability for visible light. Therefore, a systematic series of four novel heteroleptic Cu(I) complexes of the type [(P^P)Cu(N^N)]+ (with P^P = xantphos and N^N = different diimine ligands) has been prepared. As an essential feature, these copper photosensitizers contain an imidazole moiety at the backbone of the diimine ligand, which increases the aromatic π-system compared to phenanthroline type ligands. Moreover, 2-(4-bromophenyl)-1-phenyl-1H-imidazo-[4,5-f][1,10]phenanthroline was used as a starting point and modular platform for gradually extended diimine ligands. Suzuki cross-coupling was applied to introduce different kind of substituents in the back of this ligand. Afterwards, a combination of NMR spectroscopy, mass spectrometry, X-ray analysis, cyclic voltammetry, UV/vis and emission spectroscopy was used to investigate the structural, electrochemical and photophysical properties of these compounds. As a result, a reversible reduction, strongly increased extinction coefficients and significantly redshifted absorption maxima (>20 nm) were found compared to traditional Cu(I) photosensitizers without an imidazo moiety. Moreover, these compounds show a bright emission in the solid state.