Multiple Triplet Metal-Centered Jahn-Teller Isomers Determine Temperature-Dependent Luminescence Lifetimes in [Ru(bpy)3 ]2.

Understanding the factors that determine the luminescence lifetime of transition metal compounds is key for applications in photocatalysis and photodynamic therapy. Here we show that for [ Ru ( bpy ) 3 ] 2 + ${[{\rm{Ru}}({\rm{bpy}})_{\rm{3}} ]^{{\rm{2 + }}} }$ (bpy = 2,2'-bipyridine), the generally accepted idea that emission lifetimes can be controlled optimizing the energy barrier from the emissive triplet metal-to-ligand charge-transfer (3 MLCT) state to the thermally-activated triplet metal-centered (3 MC) state or the energy gap between both states is a misconception. Further, we demonstrate that considering a single relaxation pathway determined from the minimum that is lowest in energy leads to wrong temperature-dependent emission lifetimes predictions. Instead, we obtain excellent agreement with experimental temperature-dependent lifetimes when an extended kinetic model that includes all the pathways related to multiple Jahn-Teller isomers and their effective reaction barriers is employed. These concepts are essential to correctly design other luminescent transition metal complexes with tailored emission lifetimes based on theoretical predictions.

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.

Prolonged Luminescence Lifetime of a Dual Emissive Ruthenium Dipyridophenazine-Type Complex in Aprotic and Protic Solvents.

A recently reported ruthenium(II) complex bearing an extended dipyridophenazine ligand exhibits unusual long-lived dual emission at room temperature. In this study, the effect of the introduction of a methyl protecting group to the imidazole moiety of this ligand (L1, 11-methyl-11H-imidazo[4,5-i]dipyrido[3,2-a:2',3'-c]phenazine) on the photophysics of the respective ruthenium(II) complex [(tbbpy)2Ru(L1)]2+ (C1) is demonstrated by means of electrochemistry, UV/vis absorption and emission spectroscopy, as well as emission lifetime measurements, and transient absorption spectroscopy on the nanosecond time scale. At room temperature, C1 shows dual emission both in aprotic and in protic solvents with time constants of 1.1/34.2 and 1.2/8.4 µs, respectively. These lifetimes are assigned to the emission from 3MLCT and 3LC states. The introduction of the methyl group increases the lifetime of the 3LC state in C1 almost by a factor of 2 in acetonitrile solution compared to the previously reported compound. Accordingly, the newly introduced methyl group is described as a protecting group for the imidazole moiety of the heterocyclic ligand, which enables prolonged lifetimes of the dual emissive complex in protic solvents. The stabilization of the electronic structure is further underlined by the enhanced stability toward electrochemical reduction as evidenced by cyclic voltammetry.

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.

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.