Isolation, Characterization and Reactivity of Key Intermediates Relevant to Reductive (Electro)catalysis with Cp*Rh Complexes Containing Pyridyl-MIC (MIC=Mesoionic Carbene) Ligands.

In recent years, metal complexes of pyridyl-mesoionic carbene (MIC) ligands have been reported as excellent homogeneous and molecular electrocatalysts. In combination with group 9 metals, such ligands form highly active catalysts for hydrogenation/transfer hydrogenation/hydrosilylation catalysis and electrocatalysts for dihydrogen production. Despite such progress, very little is known about the structural/electrochemical/spectroscopic properties of crucial intermediates for such catalytic reactions with these ligands: solvato complexes, reduced complexes and hydridic species. We present here a comprehensive study involving the isolation, crystallographic characterization, electrochemical/spectroelectrochemical/theoretical investigations, and in-situ reactivity studies of all the aforementioned crucial intermediates involving Cp*Rh and pyridyl-MIC ligands. A detailed mechanistic study of the precatalytic activation of [RhCp*] complexes with pyridyl-MIC ligands is presented. Intriguingly, amphiphilicity of the [RhCp*]-hydride complexes was observed, displaying the substrate dependent transfer of H+ , H or H- . To the best of our knowledge, this study is the first of its kind targeting intermediates and reactive species involving metal complexes of pyridyl-MIC ligands and investigating the interconversion amongst them.

The Best of Both Worlds: Combining the Power of MICs and WCAs To Generate Stable and Crystalline CrI -Tetracarbonyl Complexes with π-Accepting Ligands.

Invited for the cover of this issue are Biprajit Sarkar and co-workers at the University of Stuttgart and University of Freiburg. In the image, the solar flare represents the non-innocence (fluorine-specific interactions) of the counterion, and the black hole at the metal center illustrates the oxidation/electron deficiency of the Cr-center, while the electron "gets lost" in the space (oxidation agent). Read the full text of the article at 10.1002/chem.202301205.

The Best of Both Worlds: Combining the Power of MICs and WCAs To Generate Stable and Crystalline CrI -Tetracarbonyl Complexes with π-Accepting Ligands.

Here we present stable and crystalline chromium(I) tetracarbonyl complexes with pyridyl-MIC (MIC=mesoionic carbene) ligands and weakly coordinating anions (WCA=[Al(ORF )4 ]- , RF =C(CF3 )3 and BArF =[B(ArF )4 ]- , ArF =3,5-(CF3 )2 C6 H3 ). The complexes were fully characterized via crystallographic, spectroscopic and theoretical methods. The influence of counter anions on the IR and EPR spectroscopic properties of the CrI complexes was investigated, and the electronic innocence versus non-innocence of WCAs was probed. These are the first examples of stable and crystalline [Cr(CO)4 ]+ complexes with a chelating π - ${\pi -}$ accepting ligand, and the data presented here are of relevance for both the photochemical and the electrochemical properties of these classes of compounds.

Spin Crossover and Fluorine-Specific Interactions in Metal Complexes of Terpyridines with Polyfluorocarbon Tails.

In coordination chemistry and materials science, terpyridine ligands are of great interest, due to their ability to form stable complexes with a broad range of transition metal ions. We report three terpyridine ligands containing different perfluorocarbon (PFC) tails on the backbone and the corresponding FeII and CoII complexes. The CoII complexes display spin crossover close to ambient temperature, and the nature of this spin transition is influenced by the length of the PFC tail on the ligand backbone. The electrochemical properties of the metal complexes were investigated with cyclic voltammetry revealing one oxidation and several reduction processes. The fluorine-specific interactions were investigated by EPR measurements. Analysis of the EPR spectra of the complexes as microcrystalline powders and in solution reveals exchange-narrowed spectra without resolved hyperfine splittings arising from the 59 Co nucleus; this suggests complex aggregation in solution mediated by interactions of the PFC tails. Interestingly, addition of perfluoro-octanol in different ratios to the acetonitrile solution of the sample resulted in the disruption of the F ⋯ ${\cdots }$ F interactions of the tails. To the best of our knowledge, this is the first investigation of fluorine-specific interactions in metal complexes through EPR spectroscopy, as exemplified by exchange narrowing.

A Different Perspective on Tuning the Photophysical and Photochemical Properties: The Influence of Constitutional Isomers in Group 6 Carbonyl Complexes with Pyridyl-Mesoionic Carbenes.

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.

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.

Liquid crystalline self-assembly of azulene-thiophene hybrids and their applications as OFET materials.

Orientational control within thin films is crucial for the preparation of organic field effect transistors (OFETs). The highly ordered liquid crystalline smectic E phase (SmE) is known as a powerful template for solution processed thin films. Here, we describe the synthesis and characterization of three novel azulene-thiophene hybrid materials. Liquid crystalline characterization showed the presence of wide SmE phases. Thin films were prepared by spin-coating at mesophase temperature. Due to the self-aligning properties of the SmE phase uniformly flat films with good molecular alignment were manufactured. Top contact bottom gate OFETs showed mobilities up to (3.3 ± 0.5) × 10-3 cm2 V-1 s-1.

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.

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.

2-(Trimethylsilyl)-λ3 -Phosphinine: Synthesis, Coordination Chemistry, and Reactivity.

The [4+2] cycloaddition reaction between 2-pyrone and Me3 Si-C≡P gives the corresponding 2-(trimethylsilyl)-λ3 -phosphinine in good yields as a rather air and moisture stable, colorless oil. Insight into the regioselectivity of the pericyclic reaction was obtained with the help of deuterium-labeling experiments. The silyl-phosphinine acts as a ligand for the preparation of a Cu(I) and the first crystallographically characterized phosphinine-Ag(I) complex. The title compound was further used as a starting material for an alternative preparation of the parent phosphinine C5 H5 P by means of protodesilylation with HCl. C5 H5 P reacts with CuBr⋅S(CH3 )2 to give an infinite Cu(I)Br coordination polymer. DFT calculations shed light on the influence of the -Si(CH3 )3 group on the electronic properties of the aromatic phosphorus heterocycle.

Impact of Bidentate Pyridyl-Mesoionic Carbene Ligands: Structural, (Spectro)Electrochemical, Photophysical, and Theoretical Investigations on Ruthenium(II) Complexes.

We present here new synthetic strategies for the isolation of a series of Ru(II) complexes with pyridyl-mesoionic carbene ligands (MIC) of the 1,2,3-triazole-5-ylidene type, in which the bpy ligands (bpy = 2,2'-bipyridine) of the archetypical [Ru(bpy)3]2+ have been successively replaced by one, two, or three pyridyl-MIC ligands. Three new complexes have been isolated and investigated via NMR spectroscopy and single-crystal X-ray diffraction analysis. The incorporation of one MIC unit shifts the potential of the metal-centered oxidation about 160 mV to more cathodic potential in cyclic voltammetry, demonstrating the extraordinary σ-donor ability of the pyridyl-MIC ligand, while the π-acceptor capacities are dominated by the bpy ligand, as indicated by electron paramagnetic resonance spectroelectrochemistry (EPR-SEC). The replacement of all bpy ligands by the pyridyl-MIC ligand results in an anoidic shift of the ligand-centered reduction by 390 mV compared to the well-established [Ru(bpy)3]2+ complex. In addition, UV/vis/NIR-SEC in combination with theoretical calculations provided detailed insights into the electronic structures of the respective redox states, taking into account the total number of pyridyl-MIC ligands incorporated in the Ru(II) complexes. The luminescence quantum yield and lifetimes were determined by time-resolved absorption and emission spectroscopy. An estimation of the excited state redox potentials conclusively showed that the pyridyl-MIC ligand can tune the photoredox activity of the isolated complexes to stronger photoreductants. These observations can provide new strategies for the design of photocatalysts and photosensitizers based on MICs.

A crystalline cyclic (alkyl)(amino)carbene with a 1,1'-ferrocenylene backbone.

Cyclic (alkyl)(amino)carbenes with a 1,1'-ferrocenylene backbone (fcCAACs) are established as an original family by the preparation of a crystalline congener. The Ccarbene bond angle is unprecedentedly wide for a CAAC, causing an exceptionally pronounced ambiphilicity. The redox-active backbone opens the door to unconventional metalloradicals and oligoradicals.

Fluorinated click-derived tripodal ligands drive spin crossover in both iron(II) and cobalt(II) complexes.

Control of the spin state of metal complexes is important because it leads to a precise control over the physical properties and the chemical reactivity of the metal complexes. Currently, controlling the spin state in metal complexes is challenging because a precise control of the properties of the secondary coordination sphere is often difficult. It has been shown that non-covalent interactions in the secondary coordination sphere of transition metal complexes can enable spin state control. Here we exploit this strategy for fluorinated triazole ligands and present mononuclear CoII and FeII complexes with "click"-derived tripodal ligands that contain mono-fluorinated benzyl substituents on the backbone. Structural characterization of 1 and 2 at 100 K revealed Co-N bond lengths that are typical of high spin (HS) CoII complexes. In contrast, the Fe-N bond lengths for 3 are characteristic of a low spin (LS) FeII state. All complexes show an intramolecular face-to-face non-covalent interaction between two arms of the ligand. The influence of the substituents and of their geometric structure on the spin state of the metal center was investigated through SQUID magnetometry, which revealed spin crossover occurring in compounds 1 and 3. EPR spectroscopy sheds further light on the electronic structures of 1 and 2 in their low- and high-spin states. Quantum-chemical calculations of the fluorobenzene molecule were performed to obtain insight into the influence of fluorine-specific interactions. Interestingly, this work shows that the same fluorinated tripodal ligands induce SCO behavior in both FeII and CoII complexes.

Oxidative access via aqua regia to an electrophilic, mesoionic dicobaltoceniumyltriazolylidene gold(III) catalyst.

A gold(III) complex with the hitherto most electron poor mesoionic carbene ligand is presented. Aqua regia was the oxidizing agent of choice for the synthesis of this unusual organometallic compound. The AuIII complex is redox-rich, and also acts as a catalyst for oxazole formation, delivering selectively a completely different isomer compared to its AuI congener.