Mechanistic and Kinetic Investigations of ON/OFF (Photo)Switchable Binding of Carbon Monoxide by Chromium(0), Molybdenum(0) and Tungsten(0) Carbonyl Complexes with a Pyridyl-Mesoionic Carbene Ligand.

This work tackles the photochemistry of a series of mononuclear Cr0 , Mo0 and W0 carbonyl complexes containing a bidentate mesoionic carbene ligand of the 1,2,3-triazol-5-ylidene type. FTIR spectroscopy, combined with density functional theory calculations, revealed a clean photo-induced reaction in organic solvents (acetonitrile, pyridine, valeronitrile) to give mainly one photoproduct with monosubstitution of a carbonyl ligand for a solvent molecule. The highest photodissociation quantum yields were reached for the Cr0 complex under UV irradiation (266 nm). Based on previous investigations, the kinetics of the dark reverse reactions have now been determined, with reaction times of up to several hours in pyridine. Photochemical studies in the solid state (KBr matrix, frozen solution) also showed light-induced reactivity with stabilization of the metastable intermediate with a free coordination site at very low temperature. The identified reactive species emphasizes a mechanism without ligand-sphere reorganization.

Mechanistic and Kinetic Investigations of ON/OFF (Photo)Switchable Binding of Carbon Monoxide by Chromium(0), Molybdenum(0) and Tungsten(0) Carbonyl Complexes with a Pyridyl-Mesoionic Carbene Ligand.

Invited for the cover of this issue are Gereon Niedner-Schatteburg, Biprajit Sarkar and co-worker at TU Kaiserslautern and the University of Stuttgart. The image depicts the selective dissociation of an axial CO from a metal complex. Read the full text of the article at 10.1002/chem.202201038.

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.

NIR-Emissive Chromium(0), Molybdenum(0), and Tungsten(0) Complexes in the Solid State at Room Temperature.

The development of NIR emitters based on earth-abundant elements is an important goal in contemporary science. We present here Cr(0), Mo(0), and W(0) carbonyl complexes with a pyridyl-mesoionic carbene (MIC) based ligand. A detailed photophysical investigation shows that all the complexes exhibit dual emissions in the VIS and in the NIR region. The emissive excited states are assigned to two distinct triplet states by time-resolved emission and step-scan FTIR spectroscopy at variable temperature, supported by density functional theory. In particular, the NIR emissive triplet state exhibits unprecedented lifetimes of up to 600±10 ns and quantum yields reaching 1.7 ⋅ 10-4 at room temperature. These are the first examples of Cr(0), Mo(0) and W(0) complexes that emit in the NIR II region.

Time-Resolved Spectroscopy and Electronic Structure of Mono-and Dinuclear Pyridyl-Triazole/DPEPhos-Based Cu(I) Complexes.

Chemical and spectroscopic characterization of the mononuclear photosensitizers [(DPEPhos)Cu(I)(MPyrT)]0/+ (CuL, CuLH) and their dinuclear analogues (Cu2 L', Cu2 L'H2 ), backed by (TD)DFT and high-level GW-Bethe-Salpeter equation calculations, exemplifies the complex influence of charge, nuclearity and structural flexibility on UV-induced photophysical pathways. Ultrafast transient absorption and step-scan FTIR spectroscopy reveal flattening distortion in the triplet state of CuLH as controlled by charge, which also appears to have a large impact on the symmetry of the long-lived triplet states in Cu2 L' and Cu2 L'H2 . Time-resolved luminescence spectroscopy (solid state), supported by transient photodissociation spectroscopy (gas phase), confirm a lifetime of some tens of µs for the respective triplet states, as well as the energetics of thermally activated delayed luminescence, both being essential parameters for application of these materials based on earth-abundant copper in photocatalysis and luminescent devices.

Investigation of Luminescent Triplet States in Tetranuclear CuI Complexes: Thermochromism and Structural Characterization.

To develop new and flexible CuI containing luminescent substances, we extend our previous investigations on two metal-centered species to four metal-centered complexes. These complexes could be a basis for designing new organic light-emitting diode (OLED) relevant species. Both the synthesis and in-depth spectroscopic analysis, combined with high-level theoretical calculations are presented on a series of tetranuclear CuI complexes with a halide containing Cu4 X4 core (X=iodide, bromide or chloride) and two 2-(diphenylphosphino)pyridine bridging ligands with a methyl group in para (4-Me) or ortho (6-Me) position of the pyridine ring. The structure of the electronic ground state is characterized by X-ray diffraction, NMR, and IR spectroscopy with the support of theoretical calculations. In contrast to the para system, the complexes with ortho-substituted bridging ligands show a remarkable and reversible temperature-dependent dual phosphorescence. Here, we combine for the first time the luminescence thermochromism with time-resolved FTIR spectroscopy. Thus, we receive experimental data on the structures of the two triplet states involved in the luminescence thermochromism. The transient IR spectra of the underlying triplet metal/halide-to-ligand charge transfer (3 M/XLCT) and cluster-centered (3 CC) states were obtained and interpreted by comparison with calculated vibrational spectra. The systematic and significant dependence of the bridging halides was analyzed.

Transient FTIR spectroscopy after one- and two-colour excitation on a highly luminescent chromium(III) complex.

The development of photoactive transition metal complexes with Earth-abundant metals is a rapidly growing research field, where a deeper understanding of the underlying photophysical processes is of great importance. A multitude of potential applications in the fields of photosensitizing, optical sensing, photoluminescence and photoredox catalysis motivates demanding spectroscopic studies. We applied a series of high-level spectroscopic methods on the previously reported highly luminescent chromium(iii) complex [Cr(ddpd)2](BF4)3 (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine) possessing two near-IR emissive doublet states with microsecond lifetimes. Luminescence measurements were performed at temperatures down to about 10 K, showing a remarkable rise of the integrated emission intensity by more than a factor of three. The emissive doublet states were structurally characterized by transient FTIR spectroscopy at 290 K and 20 K, supplemented by ground state FTIR and Raman spectroscopy in combination with density functional theory. According to emission and step-scan FT-IR spectroscopy, the stronger luminescence at lower temperature arises from decreased non-radiative decay via energy transfer to CH vibrational overtones and increased radiative decay based on lowered symmetry. Pump/pump/probe (FTIR) and pump/dump/probe (FTIR) schemes were developed to modulate the excited doublet state populations at 290 and 20 K as a function of specific near-IR pump vs. dump wavelengths. The effect of the second near-IR pulse can be explained by combinations of excited state absorption, ground state absorption and stimulated emission. The successful establishment of these two-colour step-scan FTIR experiments is an important step towards profound studies on further transition metal complexes with energetically close-lying excited states in the near future.

Structural Characterization and Lifetimes of Triple-Stranded Helical Coinage Metal Complexes: Synthesis, Spectroscopy and Quantum Chemical Calculations.

This work reports on a series of polynuclear complexes containing a trinuclear Cu, Ag, or Au core in combination with the fac-isomer of the metalloligand [Ru(pypzH)3 ](PF6 )2 (pypzH=3-(pyridin-2-yl)pyrazole). These (in case of the Ag and Au containing species) newly synthesized compounds of the general formula [{Ru(pypz)3 }2 M3 ](PF6 ) (2: M=Cu; 3: M=Ag; 4: M=Au) contain triple-stranded helical structures in which two ruthenium moieties are connected by three N-M-N (M=Cu, Ag, Au) bridges. In order to obtain a detailed description of the structure both in the electronic ground and excited states, extensive spectroscopic and quantum chemical calculations are applied. The equilateral coinage metal core triangle in the electronic ground state of 2-4 is distorted in the triplet state. Furthermore, the analyses offer a detailed description of electronic excitations. By using time-resolved IR spectroscopy from the microsecond down to the nanosecond regime, both the vibrational spectra and the lifetime of the lowest lying electronically excited triplet state can be determined. The lifetimes of these almost only non-radiative triplet states of 2-4 show an unusual effect in a way that the Au-containing complex 4 has a lifetime which is by more than a factor of five longer than in case of the Cu complex 2. Thus, the coinage metals have a significant effect on the electronically excited state, which is localized on a pypz ligand coordinated to the Ru atom indicating an unusual cooperative effect between two moieties of the complex.

Chromium(0) and Molydenum(0) Complexes with a Pyridyl-Mesoionic Carbene Ligand: Structural, (Spectro)electrochemical, Photochemical, and Theoretical Investigations.

This work reports on the synthesis and in-depth electrochemical and photochemical characterization of two chromium(0) and molydenum(0) metal complexes with bidentate pyridyl-mesoionic carbene (MIC) ligands of the 1,2,3-triazol-5-ylidene type and carbonyl coligands. Metal complexes with MIC ligands have turned out to have very promising electrocatalytic and photochemical properties, but examples of MIC-containing complexes with early-transition-metal centers remain extremely rare. The electrochemistry of these new MIC complexes was studied by cyclic voltammetry and especially spectroelectrochemistry in the IR region consistent with a mainly metal-centered oxidation, which is fully reversible in the case of the chromium(0) complex. At the same time, the two reduction steps are predominantly ligand-centered according to the observed near-IR absorbance, with the first reduction step being reversible for both systems. The results of the electron paramagnetic resonance studies on the oxidized and reduced species confirm the IR spectroelectrochemistry experiments. The photochemical reactivity of the complexes with a series of organic ligands was investigated by time-resolved (step-scan) Fourier transform infrared (FTIR) spectroscopy. Interestingly, the photoreactions in pyridine and acetonitrile are fully reversible with a slow dark reverse reaction back to the educt species over minutes and even hours, depending on the metal center and reagent. This reversible behavior is in contrast to the expected loss of one or several CO ligands known from related homoleptic as well as heteroleptic M(CO)4L2 α-diimine transition-metal complexes.

Deuterated Molecular Ruby with Record Luminescence Quantum Yield.

The recently reported luminescent chromium(III) complex 13+ ([Cr(ddpd)2 ]3+ ; ddpd=N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine) shows exceptionally strong near-IR emission at 775 nm in water under ambient conditions (Φ=11 %) with a microsecond lifetime as the ligand design in 13+ effectively eliminates non-radiative decay pathways, such as photosubstitution, back-intersystem crossing, and trigonal twists. In the absence of energy acceptors, such as dioxygen, the remaining decay pathways are energy transfer to high energy solvent and ligand oscillators, namely OH and CH stretching vibrations. Selective deuteration of the solvents and the ddpd ligands probes the efficiency of these oscillators in the excited state deactivation. Addressing these energy-transfer pathways in the first and second coordination sphere furnishes a record 30 % quantum yield and a 2.3 millisecond lifetime for a metal complex with an earth-abundant metal ion in solution at room temperature.

Intermetallic Competition in the Fragmentation of Trimetallic Au-Zn-Alkali Complexes.

Cationization is a valuable tool to enable mass spectrometric studies on neutral transition-metal complexes (e.g., homogenous catalysts). However, knowledge of potential impacts on the molecular structure and catalytic reactivity induced by the cationization is indispensable to extract information about the neutral complex. In this study, we cationize a bimetallic complex [AuZnCl3 ] with alkali metal ions (M(+) ) and investigate the charged adducts [AuZnCl3 M](+) by electrospray ionization mass spectrometry (ESI-MS). Infrared multiple photon dissociation (IR-MPD) in combination with density functional theory (DFT) calculations reveal a µ(3) binding motif of all alkali ions to the three chlorido ligands. The cationization induces a reorientation of the organic backbone. Collision-induced dissociation (CID) studies reveal switches of fragmentation channels by the alkali ion and by the CID amplitude. The Li(+) and Na(+) adducts prefer the sole loss of ZnCl2 , whereas the K(+) , Rb(+) , and Cs(+) adducts preferably split off MCl2 ZnCl. Calculated energetics along the fragmentation coordinate profiles allow us to interpret the experimental findings to a level of subtle details. The Zn(2+) cation wins the competition for the nitrogen coordination sites against K(+) , Rb(+) , and Cs(+) , but it loses against Li(+) and Na(+) in a remarkable deviation from a naive hard and soft acids and bases (HSAB) concept. The computations indicate expulsion of MCl2 ZnCl rather than of MCl and ZnCl2 .

An intermolecular C-H oxidizing strategy to access highly fused carbazole skeletons from simple naphthylamines.

Highly π-extended hetero-cyclic/aromatic skeletons are of great importance as they can be utilized in many organic material based technologies. Therefore, developing efficient, pre-activation-free, synthetic procedures for the rapid build-up of these complex structures remains a high priority objective. The herein presented approach delivers highly fused carbazole skeletons from simple naphthylamine derivatives.

Highly soluble fluorine containing Cu(i) AlkylPyrPhos TADF complexes.

Luminescent Cu(i) AlkylPyrPhos complexes with a butterfly-shaped Cu2I2 core and halogen containing ancillary ligands, with a special focus on fluorine, have been investigated in this study. These complexes show extremely high solubilities and a remarkable (photo)chemical stability in a series of solvents. A tunable emission resulting from thermally activated delayed fluorescence with high quantum yields was determined by luminescence and lifetime investigations in solvents and solids. Structures of the electronic ground states were analyzed by single crystal X-ray analysis. The structure of the lowest excited triplet state was determined by transient FTIR spectroscopy, in combination with quantum chemical calculations. With the obtained range of compounds we address the key requirement for the production of organic light emitting diodes based on solution processing.