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In this report, we present the dinuclear copper(II) dimethylglyoxime (H2 dmg) complex [Cu2 (H2 dmg)(Hdmg)(dmg)]+ (1), which, in contrast to its mononuclear analogue [Cu(Hdmg)2 ] (2), is subject to a cooperativity-driven hydrolysis. The combined Lewis acidity of both copper centers increases the electrophilicity of the carbon atom in the bridging µ2 -O-N=C-group of H2 dmg and thus, facilitates the nucleophilic attack of H2 O. This hydrolysis yields butane-2,3-dione monoxime (3) and NH2 OH that, depending on the solvent, is then either oxidized or reduced. In ethanol, NH2 OH is reduced to NH4 + , yielding acetaldehyde as the oxidation product. In contrast, in CH3 CN, NH2 OH is oxidized by CuII to form N2 O and [Cu(CH3 CN)4 ]+ . Herein are presented the combined synthetic, theoretical, spectroscopic and spectrometric methods that indicate and establish the reaction pathway of this solvent-dependent reaction.
RESUMO
Exploring novel and existing design principles to tune the photochemical and photophysical properties of transition-metal complexes is an important goal in contemporary research. Here, we highlight the influence of constitutional isomers of pyridyl-1,2,3-triazolylidene mesoionic carbene (MIC) ligands on the photophysical and photochemical properties of the corresponding tetracarbonyl group 6 metal complexes (M = Cr, Mo, W). All new complexes [M(C-C)] presented herein incorporate a C-C linked pyridyl-MIC ligand and were fully characterized by X-ray diffraction analysis, elemental analysis, and 1H NMR and IR spectroscopy. Detailed photophysical investigations reveal a single emission in the VIS region, which extends into the NIR with lifetimes of up to 3.5 µs in the solid state at lower temperatures. The quantum yields were determined for all three complexes, and, in particular, the W0 complex shows an unusually high quantum yield of 29% compared to the values of 0.02% obtained for the [M(C-N)] isomers investigated in earlier works. Beyond this, the investigated W0 complex also exhibits an emission at 717 nm in a fluid solution. The combination of luminescence and FTIR-step scan spectroscopy with theoretical calculations reveals an emissive 3MLCT state. Irradiation of the presented complexes leads to a clean cleavage of one axial CO ligand. A metastable 16 VE species with a vacant axial coordination site was detected in the solid state at low temperatures. In solution, the respective solvato complexes are formed. A dark reverse reaction is observed, as previously described for the [M(C-N)] analogues. The increased electron density induced by the C-C linked pyridyl-MIC ligand leads to an increased kinetic rate constant for the reformation of the starting species and is also reflected in the lower photodissociation quantum yields.
RESUMO
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.
RESUMO
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 (266â 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.
RESUMO
The synthesis of copper and zinc complexes of four variably substituted iminophosphonamide ligands is presented. While the copper complexes form ligand-bridged dimers, the zinc compounds are monomeric. Due to different steric demand of the ligand the arrangement of the ligands within the dimeric complexes varies. Similar to the structurally related iminophosphonamide complexes of alkali metals and calcium, the steady-state and time-resolved photoluminescence (PL) of four of the seven compounds studied here as solids in a temperature range of 5-295â K can be described within the scheme of thermally activated delayed fluorescence (TADF). Accordingly, they exhibit bright blue-green phosphorescence at low temperatures (<100â K), which turns into delayed fluorescence by increasing the temperature. However, unusually, the fluorescence is practically absent in two copper complexes which otherwise still conform to the TADF scheme. In these cases, the excited singlet states decay essentially non-radiatively and their thermal population from the corresponding low-lying triplet states efficiently quenches PL (phosphorescence). Three other copper and zinc complexes only exhibit prompt fluorescence, evidencing a wide variation of photophysical properties in this class of compounds. The excited states of the copper complex with especially pronounced phosphorescence quenching were also investigated by low-temperature time-resolved infrared spectroscopy and quantum chemical calculations.