Precious-Metal-Free CO2 Photoreduction Boosted by Dynamic Coordinative Interaction between Pyridine-Tethered Cu(I) Sensitizers and a Co(II) Catalyst.

Improving the photocatalytic efficiency of a fully noble-metal-free system for CO2 reduction remains a fundamental challenge, which can be accomplished by facilitating electron delivery as a consequence of exploiting intermolecular interactions. Herein, we have designed two Cu(I) photosensitizers with different pyridyl pendants at the phenanthroline moiety to enable dynamic coordinative interactions between the sensitizers and a cobalt macrocyclic catalyst. Compared to the parent Cu(I) photosensitizer, one of the pyridine-tethered derivatives boosts the apparent quantum yield up to 76 ± 6% at 425 nm for selective (near 99%) CO2-to-CO conversion. This value is nearly twice that of the parent system with no pyridyl pendants (40 ± 5%) and substantially surpasses the record (57%) of the noble-metal-free systems reported so far. This system also realizes a maximum turnover number of 11 800 ± 1400. In contrast, another Cu(I) photosensitizer, in which the pyridine substituents are directly linked to the phenanthroline moiety, is inactive. The above behavior and photocatalytic mechanism are systematically elucidated by transient fluorescence, transient absorption, transient X-ray absorption spectroscopies, and quantum chemical calculations. This work highlights the advantage of constructing coordinative interactions to fine-tune the electron transfer processes within noble-metal-free systems for CO2 photoreduction.

Bichromophoric Photosensitizers: How and Where to Attach Pyrene Moieties to Phenanthroline to Generate Copper(I) Complexes.

Pyrene is a polycyclic aromatic hydrocarbon and organic dye that can form superior bichromophoric systems when combined with a transition metal-based chromophore. However, little is known about the effect of the type of attachment (i.e., 1- vs 2-pyrenyl) and the individual position of the pyrenyl substituents at the ligand. Therefore, a systematic series of three novel diimine ligands and their respective heteroleptic diimine-diphosphine copper(I) complexes has been designed and extensively studied. Special attention was given to two different substitution strategies: (i) attaching pyrene via its 1-position, which occurs most frequently in the literature, or via its 2-position and (ii) targeting two contrasting substitution patterns at the 1,10-phenanthroline ligand, i.e., the 5,6- and the 4,7-position. In the applied spectroscopic, electrochemical, and theoretical methods (UV/vis, emission, time-resolved luminescence and transient absorption, cyclic voltammetry, density functional theory), it has been shown that the precise choice of the derivatization sites is crucial. Substituting the pyridine rings of phenanthroline in the 4,7-position with the 1-pyrenyl moiety has the strongest impact on the bichromophore. This approach results in the most anodically shifted reduction potential and a drastic increase in the excited state lifetime by more than two orders of magnitude. In addition, it enables the highest singlet oxygen quantum yield of 96% and the most beneficial activity in the photocatalytic oxidation of 1,5-dihydroxy-naphthalene.

Homoleptic Al(III) Photosensitizers for Durable CO2 Photoreduction.

Exploiting noble-metal-free systems for high-performance photocatalytic CO2 reduction still presents a key challenge, partially due to the long-standing difficulties in developing potent and durable earth-abundant photosensitizers. Therefore, based on the very cheap aluminum metal, we have deployed a systematic series of homoleptic Al(III) photosensitizers featuring 2-pyridylpyrrolide ligands for CO2 photoreduction. The combined studies of steady-state and time-resolved spectroscopy as well as quantum chemical calculations demonstrate that in anerobic CH3CN solutions at room temperature, visible-light excitation of the Al(III) photosensitizers leads to an efficient population of singlet excited states with nanosecond-scale lifetimes and notable emission quantum yields (10-40%). The results of transient absorption spectroscopy further identified the presence of emissive singlet and unexpectedly nonemissive triplet excited states. More importantly, the introduction of methyl groups at the pyrrolide rings can greatly improve the visible-light absorption, reducing power, and durability of the Al(III) photosensitizers. With triethanolamine, BIH (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole), and an Fe(II)-quaterpyridine catalyst, the most methylated Al(III) photosensitizer achieves an apparent quantum efficiency of 2.8% at 450 nm for selective (>99%) CO2-to-CO conversion, which is nearly 28 times that of the unmethylated one (0.1%) under identical conditions. The optimal system realizes a maximum turnover number of 10250 and higher robustness than the systems with Ru(II) and Cu(I) benchmark photosensitizers. Quenching experiments using fluorescence spectroscopy elucidate that the photoinduced electron transfer in the Al(III)-sensitized system follows a reductive quenching pathway. The remarkable tunability and cost efficiency of these Al(III) photosensitizers should allow them as promising components in noble-metal-free systems for solar fuel conversion.

How the Way a Naphthalimide Unit is Implemented Affects the Photophysical and -catalytic Properties of Cu(I) Photosensitizers.

Driven by the great potential of solar energy conversion this study comprises the evaluation and comparison of two different design approaches for the improvement of copper based photosensitizers. In particular, the distinction between the effects of a covalently linked and a directly fused naphthalimide unit was assessed. For this purpose, the two heteroleptic Cu(I) complexes CuNIphen (NIphen = 5-(1,8-naphthalimide)-1,10-phenanthroline) and Cubiipo (biipo = 16H-benzo-[4',5']-isoquinolino-[2',1',:1,2]-imidazo-[4,5-f]-[1,10]-phenanthroline-16-one) were prepared and compared with the novel unsubstituted reference compound Cuphen (phen = 1,10-phenanthroline). Beside a comprehensive structural characterization, including two-dimensional nuclear magnetic resonance spectroscopy and X-ray analysis, a combination of electrochemistry, steady-state and time-resolved spectroscopy was used to determine the electrochemical and photophysical properties in detail. The nature of the excited states was further examined by (time-dependent) density functional theory (TD-DFT) calculations. It was found that CuNIphen exhibits a greatly enhanced absorption in the visible and a strong dependency of the excited state lifetimes on the chosen solvent. For example, the lifetime of CuNIphen extends from 0.37 µs in CH2Cl2 to 19.24 µs in MeCN, while it decreases from 128.39 to 2.6 µs in Cubiipo. Furthermore, CuNIphen has an exceptional photostability, allowing for an efficient and repetitive production of singlet oxygen with quantum yields of about 32%.

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.

Merging of a Perylene Moiety Enables a RuII Photosensitizer with Long-Lived Excited States and the Efficient Production of Singlet Oxygen.

Invited for the front cover of this issue are Stefanie Tschierlei, Sven Rau and co-workers. The image shows the fusion of an organic chromophore with a RuII polypyridine moiety resulting in a unique bichromophoric photosensitizer. Read the full text of the article at 10.1002/chem.202103609.

Merging of a Perylene Moiety Enables a RuII Photosensitizer with Long-Lived Excited States and the Efficient Production of Singlet Oxygen.

Multichromophoric systems based on a RuII polypyridine moiety containing an additional organic chromophore are of increasing interest with respect to different light-driven applications. Here, we present the synthesis and detailed characterization of a novel RuII photosensitizer, namely [(tbbpy)2 Ru((2-(perylen-3-yl)-1H-imidazo[4,5-f][1,10]-phenanthrolline))](PF6 )2 RuipPer, that includes a merged perylene dye in the back of the ip ligand. This complex features two emissive excited states as well as a long-lived (8 µs) dark state in acetonitrile solution. Compared to prototype [(bpy)3 Ru]2+ -like complexes, a strongly altered absorption (ϵ=50.3×103  M-1 cm-1 at 467 nm) and emission behavior caused by the introduction of the perylene unit is found. A combination of spectro-electrochemistry and time-resolved spectroscopy was used to elucidate the nature of the excited states. Finally, this photosensitizer was successfully used for the efficient formation of reactive singlet oxygen.

Comprehensive Picture of the Excited State Dynamics of Cu(I)- and Ru(II)-Based Photosensitizers with Long-Lived Triplet States.

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.

Cross-Coupled Phenyl- and Alkynyl-Based Phenanthrolines and Their Effect on the Photophysical and Electrochemical Properties of Heteroleptic Cu(I) Photosensitizers.

With the aims of increasing the antenna system and improving the photophysical properties of Cu(I)-based photosensitizers, the backbone of 2,9-dimethyl-1,10-phenanthroline was selectively extended in the 5,6-position. Applying specifically tailored Suzuki-Miyaura and "chemistry-on-the-complex" Sonogashira cross-coupling reactions enabled the development of two sets of structurally related diimine ligands with a broad variety of different phenyl- and alkynyl-based substituents. The resulting 11 novel heteroleptic Cu(I) complexes, including five solid-state structures, were studied with respect to their structure-property relationships. Both sets of substituents are able to red-shift the absorption maxima and to increase the absorptivity. For the alkynyl-based complexes, this is accompanied by a significant anodic shift of the reduction potentials. The phenyl-based substituents strongly influence the emission wavelength and quantum yield of the resulting Cu(I) complexes and lead to an increase in the emission lifetime of up to 504 ns, which clearly indicates competition with the benchmark system [(xantphos)Cu(bathocuproine)]PF6.

Electron Storage Capability and Singlet Oxygen Productivity of a RuII Photosensitizer Containing a Fused Naphthaloylenebenzene Moiety at the 1,10-Phenanthroline Ligand.

As a novel rylene type dye a diimine ligand with a fully rigid and extended π-system in its backbone was prepared by directly fusing a 1,10-phenanthroline building block with 1,8-naphthalimide. The corresponding heteroleptic ruthenium photosensitizer bearing one biipo and two tbbpy ligands was synthesized and extensively analyzed by a combination of NMR, single crystal X-ray diffraction, steady-state absorption and emission, time-resolved spectroscopy and different electrochemical measurements supported by time-dependent density functional theory calculations. The cyclic and differential pulse voltammograms revealed, that the naphthaloylenebenzene moiety enables an additional second reduction of the ligand. Moreover, this ligand possesses a very broad absorption in the visible region. In the RuII complex this causes an overlap of ligand-centered and metal-to-ligand charge transfer transitions. The emission of the complex is clearly redshifted compared to the ligand emission with very long-lived excited states lifetimes of 1.7 and 24.7 µs in oxygen-free acetonitrile solution. This behavior is accompanied by a surprisingly high oxygen sensitivity. Finally, this photosensitizer was successfully applied for the effective evolution of singlet oxygen challenging some of the common RuII prototype complexes.

Multidentate Phenanthroline Ligands Containing Additional Donor Moieties and Their Resulting Cu(I) and Ru(II) Photosensitizers: A Comparative Study.

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 1,10-phenanthroline ligands with either OR or SR (R = iPr 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.

The Coordination Behaviour of CuI Photosensitizers Bearing Multidentate Ligands Investigated by X-ray Absorption Spectroscopy.

A systematic series of four novel homo- and heteroleptic CuI 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.

Copper(I) Phosphinooxazoline Complexes: Impact of the Ligand Substitution and Steric Demand on the Electrochemical and Photophysical Properties.

A series of seven homoleptic CuI complexes based on hetero-bidentate P^N ligands was synthesized and comprehensively characterized. In order to study structure-property relationships, the type, size, number and configuration of substituents at the phosphinooxazoline (phox) ligands were systematically varied. To this end, a combination of X-ray diffraction, NMR spectroscopy, steady-state absorption and emission spectroscopy, time-resolved emission spectroscopy, quenching experiments and cyclic voltammetry was used to assess the photophysical and electrochemical properties. Furthermore, time-dependent density functional theory calculations were applied to also analyze the excited state structures and characteristics. Surprisingly, a strong dependency on the chirality of the respective P^N ligand was found, whereas the specific kind and size of the different substituents has only a minor impact on the properties in solution. Most importantly, all complexes except C3 are photostable in solution and show fully reversible redox processes. Sacrificial reductants were applied to demonstrate a successful electron transfer upon light irradiation. These properties render this class of photosensitizers as potential candidates for solar energy conversion issues.

Excited-state dynamics of heteroleptic copper(i) photosensitizers and their electrochemically reduced forms containing a dipyridophenazine moiety - a spectroelectrochemical transient absorption study.

The electrochemically singly-reduced Cu(i) photosensitizers of the type [Cu(xant)(N^N)]+ (with xant = xantphos ligand and N^N = bidentate diimine ligand: dipyrido[3,2-a:2',3'-c]phenazine = dppz or 3,6,11,12-tetramethyl-dipyrido[3,2-a:2',3'-c]phenazine = tmdppz) exhibit a metal-to-ligand charge transfer (MLCT) transition from the Cu(I) center to the reduced dppz˙- ligand. This special behavior makes them promising candidates for two-electron accumulation. Consequently, the photoinduced excited-state processes of [Cu(xant)(dppz)]+ (1) and [Cu(xant)(tmdppz)]+ (2) were investigated in solution by femtosecond transient absorption spectroelectrochemistry. Furthermore, the influence of the methyl substitution at the dppz ligand on the transient dynamics was revealed. Moreover, both singly-reduced species 1- and 2- possess short-lived excited states (10-20 ps) when excited into the MLCTphen or the low-lying states, representing an obstacle for the possible two-electron photoaccumulation.

Cu(i) vs. Ru(ii) photosensitizers: elucidation of electron transfer processes within a series of structurally related complexes containing an extended π-system.

Heteroleptic Cu(i) complexes are a promising alternative towards traditional Ru(ii) photosensitizers. In particular, Cu(i) complexes of the type [Cu(P^P)(N^N)]+, where N^N represents a diimine and P^P a bulky diphosphine ligand, are already successfully applied for photocatalysis, organic light-emitting diodes or dye-sensitized solar cells. Therefore, this study aims for the systematic comparison of three novel heteroleptic Cu(i) compounds, composed of xantphos (xant) as P^P ligand and different diimine ligands with an extended π-system in the backbone, with their structurally related Ru(ii) analogues. In these Ru(ii) photosensitizers [Ru(bpy)2(N^N)]2+ (bpy = 2,2'-bipyridine) the same N^N ligands were used, namely, dipyrido[3,2-f:2',3'-h]quinoxaline (dpq) and dipyrido[3,2-a:2',3'-c]phenazine (dppz). To gain an in-depth understanding of the photoinduced charge transfer processes, the photophysical features of these complexes and their electrochemically oxidized/reduced species were studied by a combination of UV-vis absorption, resonance Raman and spectroelectrochemistry. (TD)DFT calculations were applied to qualitatively analyze these measurements. As a result, the heteroleptic Cu(i) complexes exhibit comparable charge transfer properties to their Ru(ii) analogues, i.e. upon visible light excitation they undergo a metal-to-ligand charge transfer to the diimine ligand(s). In contrast, the reduced Cu(i)- and Ru(ii)-dppz complexes show considerably different electronic transitions. The singly reduced Cu(i)-dppz complexes are able to accumulate an additional electron at the phenanthroline moiety upon blue-light excitation, which is beneficial for multi-electron-transfer reactions. Upon low-energy light irradiation electronic transitions from the dppz- anion to the xant ligand are excited, which could shorten the lifetime of the photosensitizer intermediates in an unwanted way.

Morphology, Optical Properties and Photocatalytic Activity of Photo- and Plasma-Deposited Au and Au/Ag Core/Shell Nanoparticles on Titania Layers.

Titania is a promising material for numerous photocatalytic reactions such as water splitting and the degradation of organic compounds (e.g., methanol, phenol). Its catalytic performance can be significantly increased by the addition of co-catalysts. In this study, Au and Au/Ag nanoparticles were deposited onto mesoporous titania thin films using photo-deposition (Au) and magnetron-sputtering (Au and Au/Ag). All samples underwent comprehensive structural characterization by grazing incidence X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Nanoparticle distributions and nanoparticle size distributions were correlated to the deposition methods. Light absorption measurements showed features related to diffuse scattering, the band gap of titania and the local surface plasmon resonance of the noble metal nanoparticles. Further, the photocatalytic activities were measured using methanol as a hole scavenger. All nanoparticle-decorated thin films showed significant performance increases in hydrogen evolution under UV illumination compared to pure titania, with an evolution rate of up to 372 μL H2 h−1 cm−2 representing a promising approximately 12-fold increase compared to pure titania.

Elucidating the Nature of the Excited State of a Heteroleptic Copper Photosensitizer by using Time-Resolved X-ray Absorption Spectroscopy.

We report the light-induced electronic and geometric changes taking place within a heteroleptic CuI photosensitizer, namely [(xant)Cu(Me2 phenPh2 )]PF6 (xant=xantphos, Me2 phenPh2 =bathocuproine), by time-resolved X-ray absorption spectroscopy in the ps-µs time regime. Time-resolved X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis enabled the elucidation of the electronic and structural configuration of the copper center in the excited state as well as its decay dynamics in different solvent conditions with and without triethylamine acting as a sacrificial electron donor. A three-fold decrease in the decay lifetime of the excited state is observed in the presence of triethylamine, showing the feasibility of the reductive quenching pathway in the latter case. A prominent pre-edge feature is observed in the XANES spectrum of the excited state upon metal to charge ligand transfer transition, showing an increased hybridization of the 3d states with the ligand p orbitals in the tetrahedron around the Cu center. EXAFS and density functional theory illustrate a significant shortening of the Cu-N and an elongation of the Cu-P bonds together with a decrease in the torsional angle between the xantphos and bathocuproine ligand. This study provides mechanistic time-resolved understanding for the development of improved heteroleptic CuI photosensitizers, which can be used for the light-driven production of hydrogen from water.

Copper Photosensitizers Containing P

Driven by the intention to improve classic heteroleptic copper photosensitizers two novel Cu(I) complexes applying a hetero-bidentate P^N ligand were prepared. A combined photophysical, electrochemical, and theoretical study gives insights into structure-activity relationships and revealed an increased absorptivity. Both complexes were tested for the light-driven production of H2 .

Electronic and molecular structure relations in diiron compounds mimicking the [FeFe]-hydrogenase active site studied by X-ray spectroscopy and quantum chemistry.

Synthetic diiron compounds of the general formula Fe2(µ-S2R)(CO)n(L)6-n (R = alkyl or aromatic groups; L = CN- or phosphines) are versatile models for the active-site cofactor of hydrogen turnover in [FeFe]-hydrogenases. A series of 18 diiron compounds, containing mostly a dithiolate bridge and terminal ligands of increasing complexity, was characterized by X-ray absorption and emission spectroscopy in combination with density functional theory. Fe K-edge absorption and Kß main-line emission spectra revealed the varying geometry and the low-spin state of the Fe(i) centers. Good agreement between experimental and calculated core-to-valence-excitation absorption and radiative valence-to-core-decay emission spectra revealed correlations between spectroscopic and structural features and provided access to the electronic configuration. Four main effects on the diiron core were identified, which were preferentially related to variation either of the dithiolate or of the terminal ligands. Alteration of the dithiolate bridge affected mainly the Fe-Fe bond strength, while more potent donor substitution and ligand field asymmetrization changed the metal charge and valence level localization. In contrast, cyanide ligation altered all relevant properties and, in particular, the frontier molecular orbital energies of the diiron core. Mutual benchmarking of experimental and theoretical parameters provides guidelines to verify the electronic properties of related diiron compounds.

Heteroleptic Copper Photosensitizers: Why an Extended π-System Does Not Automatically Lead to Enhanced Hydrogen Production.

A series of heteroleptic copper(I) photosensitizers of the type [(P^P)Cu(N^N)]+ with an extended π-system in the backbone of the diimine ligand has been prepared. The structures of all complexes are completely characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography. These novel photosensitizers were assessed with respect to the photocatalytic reduction of protons in the presence of triethylamine and [Fe3 (CO)12 ]. Although the solid-state structures and computational results show no significant impact of the π-extension on the structural properties, decreased activities were observed. To explain this drop, a combination of electrochemical and photophysical measurements including time-resolved emission as well as transient absorption spectroscopy in the femto- to nanosecond time regime was used. Consequently, shortened excited state lifetimes caused by the rapid depopulation of the excited states located at the diimine ligand are identified as a major reason for the low photocatalytic performance.