Fundamental Characterization,Photophysics and Photocatalysis of a Base Metal Iron(II)-Cobalt(III) Dyad

A new base metal iron-cobalt dyad has been obtained by connection between a heteroleptic tetra-NHC iron(II) photosensitizer combining a 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine with 2,6-bis(3-methyl-imidazol-2-ylidene)-4,4′-bipyridine ligand, and a cobaloxime catalyst. This novel iron(II)-cobalt(III) assembly has been extensively characterized by ground- and excited-state methods like X-ray crystallography, X-ray absorption spectroscopy, (spectro-)electrochemistry, and steady-state and time-resolved optical absorption spectroscopy, with a particular focus on the stability of the molecular assembly in solution and determination of the excited-state landscape. NMR and UV/Vis spectroscopy reveal dissociation of the dyad in acetonitrile at concentrations below 1 mM and high photostability. Transient absorption spectroscopy after excitation into the metal-to-ligand charge transfer absorption band suggests a relaxation cascade originating from hot singlet and triplet MLCT states, leading to the population of the ³MLCT state that exhibits the longest lifetime. Finally, decay into the ground state involves a ³MC state. Attachment of cobaloxime to the iron photosensitizer increases the ³MLCT lifetime at the iron centre. Together with the directing effect of the linker, this potentially makes the dyad more active in photocatalytic proton reduction experiments than the analogous two-component system, consisting of the iron photosensitizer and Co(dmgH)₂(py)Cl. This work thus sheds new light on the functionality of base metal dyads, which are important for more efficient and sustainable future proton reduction systems.     

Rational Development of Guanidinate and Amidinate Based Cerium and Ytterbium Complexes as Atomic Layer Deposition Precursors: Synthesis,Modeling, and Application

Owing to the limited availability of suitable precursors for vapor phase deposition of rare-earth containing thin-film materials, new or improved precursors are sought after. In this study, we explored new precursors for atomic layer deposition (ALD) of cerium (Ce) and ytterbium (Yb) containing thin films. A series of homoleptic tris-guanidinate and tris-amidinate complexes of cerium (Ce) and ytterbium (Yb) were synthesized and thoroughly characterized. The C-substituents on the N-C-N backbone (Me, NMe₂, NEt₂, where Me=methyl, Et=ethyl) and the N-substituents from symmetrical iso-propyl (iPr) to asymmetrical tertiary-butyl (tBu) and Et were systematically varied to study the influence of the substituents on the physicochemical properties of the resulting compounds. Single crystal structures of [Ce(dpdmg)₃] 1 and [Yb(dpdmg)₃] 6 (dpdmg=N,N'-diisopropyl-2-dimethylamido-guanidinate) highlight a monomeric nature in the solid-state with a distorted trigonal prismatic geometry. The thermogravimetric analysis shows that the complexes are volatile and emphasize that increasing asymmetry in the complexes lowers their melting points while reducing their thermal stability. Density functional theory (DFT) was used to study the reactivity of amidinates and guanidinates of Ce and Yb complexes towards oxygen (O₂) and water (H₂O). Signified by the DFT calculations, the guanidinates show an increased reactivity toward water compared to the amidinate complexes. Furthermore, the Ce complexes are more reactive compared to the Yb complexes, indicating even a reactivity towards oxygen potentially exploitable for ALD purposes. As a representative precursor, the highly reactive [Ce(dpdmg)₃] 1 was used for proof-of-principle ALD depositions of CeO₂ thin films using water as co-reactant. The self-limited ALD growth process could be confirmed at 160 °C with polycrystalline cubic CeO₂ films formed on Si(100) substrates. This study confirms that moving towards nitrogen-coordinated rare-earth complexes bearing the guanidinate and amidinate ligands can indeed be very appealing in terms of new precursors for ALD of rare earth based materials.     

Switching the Mechanism of NADH Photooxidation by Supramolecular Interactions

A series of three Ru(II) polypyridine complexes was investigated for the selective photocatalytic oxidation of NAD(P)H to NAD(P)⁺ in water. A combination of (time-resolved) spectroscopic studies and photocatalysis experiments revealed that ligand design can be used to control the mechanism of the photooxidation: For prototypical Ru(II) complexes a ¹O₂ pathway was found. Rudppz ([(tbbpy)₂Ru(dppz)]Cl₂, tbbpy=4,4'-di-tert-butyl-2,2'-bipyridine, dppz=dipyrido[3,2-a:2′,3′-c]phenazine), instead, initiated the cofactor oxidation by electron transfer from NAD(P)H enabled by supramolecular binding between substrate and catalyst. Expulsion of the photoproduct NAD(P)⁺ from the supramolecular binding site in Rudppz allowed very efficient turnover. Therefore, Rudppz permits repetitive selective assembly and oxidative conversion of reduced naturally occurring nicotinamides by recognizing the redox state of the cofactor under formation of H₂O₂ as additional product. This photocatalytic process can fuel discontinuous photobiocatalysis.     

Copper‐Mediated ortho‐Nitration of (Hetero)Arenecarboxylates

Various (hetero)arenecarboxylic acids were converted to the corresponding Daugulis amides and nitrated selectively in the ortho‐position in the presence of [CuNO₃(PPh₃)₂] and AgNO₂ at 50 °C. A microwave‐assisted saponification allows regenerating the carboxylate group within minutes, which may then be removed tracelessly by protodecarboxylation, or substituted by aryl‐ or alkoxy‐groups via decarboxylative cross‐coupling.     

Aryl–Phenyl Scrambling in Intermediate Organopalladium Complexes: A Gas‐Phase Study of the Mizoroki–Heck Reaction

The intramolecular aryl–phenyl scrambling reaction within palladium–DPPP–aryl complex (DPPP=1,3‐bis(diphenylphosphino)propane) ions was analyzed by state‐of‐the‐art tandem MS, including gas‐phase ion/molecule reactions. The Mizoroki–Heck cross‐coupling reaction was performed in the gas phase, and the intrinsic reactivity of important intermediates could be examined. Moreover, linear free‐energy correlations were applied, and a mechanism for the scrambling reaction proceeding via phosphonium cations was assumed.     

Methane preconcentration by adsorption: a methodology for materials and conditions selection

Methane (CH \(_4\) ) adsorption has been widely studied, mainly in the context of natural gas purification. A much less prominent, but highly relevant application is the preconcentration of CH \(_4\) from ambient air. In this study, we compare six different commercial adsorbent materials with respect to their effectiveness for methane preconcentration: a macroporous polymeric resin (HayeSep D), multi-walled carbon nanotubes, two microporous metal-organic frameworks (HKUST-1 and ZIF-8), and two zeolites (5A and 13X). The most relevant properties, such as isosteric enthalpy of adsorption, specific surface area and the selectivity for CH \(_4\) adsorption over N \(_2\) were characterized by analyzing adsorption/desorption isotherms. Using these parameters, we discuss the tested adsorbents with respect to the most important properties and identify the most promising candidates. Furthermore we identify the experimental conditions that are expected to give the best results with respect to practical applications.     

TEAD–YAP Interaction Inhibitors and MDM2 Binders from DNA-Encoded Indole-Focused Ugi Peptidomimetics

DNA-encoded combinatorial synthesis provides efficient and dense coverage of chemical space around privileged molecular structures. The indole side chain of tryptophan plays a prominent role in key, or “hot spot”, regions of protein–protein interactions. A DNA-encoded combinatorial peptoid library was designed based on the Ugi four-component reaction by employing tryptophan-mimetic indole side chains to probe the surface of target proteins. Several peptoids were synthesized on a chemically stable hexathymidine adapter oligonucleotide “hexT”, encoded by DNA sequences, and substituted by azide-alkyne cycloaddition to yield a library of 8112 molecules. Selection experiments for the tumor-relevant proteins MDM2 and TEAD4 yielded MDM2 binders and a novel class of TEAD-YAP interaction inhibitors that perturbed the expression of a gene under the control of these Hippo pathway effectors.     

Diversity of Strontium Nitridogermanates(IV): Novel Sr4[GeN4], Sr8Ge2[GeN4], and Sr17Ge2[GeN3]2[GeN4]2

Single crystals of three new strontium nitridogermanates(IV) were grown in sealed niobium ampules from sodium flux. Dark red Sr₄[GeN₄] crystallizes in space group P2₁/c with a = 9.7923(2) Å, b = 6.3990(1) Å, c = 11.6924(3) Å and β = 115.966(1)°. Black Sr₈Ge₂[GeN₄] contains Ge^4– anions coexisting with [Ge^IVN₄]^8– tetrahedra and adopts space group Cc with a = 10.1117(4) Å, b = 17.1073(7) Å, c = 10.0473(4) Å and β = 115.966(1)°. Black Sr₁₇Ge₆N₁₄ features the same anions alongside trigonal planar [Ge^IVN₃]^5– units. It crystallizes in P1 with a = 7.5392(1) Å, b = 9.7502(2) Å, c = 11.6761(2) Å, α = 103.308(1)°, β = 94.651(1)° and γ = 110.248(1)°.     

Pyridinylidenaminophosphines: Facile Access to Highly Electron-Rich Phosphines

Electron-rich tertiary phosphines are valuable species in chemical synthesis. However, their broad application as ligands in catalysis and reagents in stoichiometric reactions is often limited by their costly synthesis. Herein, we report the synthesis and properties of a series of phosphines with 1-alkylpyridin-4-ylidenamino and 1-alkylpyridin-2-ylidenamino substituents that are accessible in a very short and scalable route starting from commercially available aminopyridines and chlorophosphines. The determination of the Tolman electronic parameter (TEP) value reveals that the electron donor ability can be tuned by the substituent pattern at the aminopyridine backbone and it can exceed that of common alkylphosphines and N-heterocyclic carbenes. The potential of the new phosphines as strong nucleophiles in phosphine-mediated transformations is demonstrated by the formation of Lewis base adducts with CO₂ and CS₂. In addition, the coordination chemistry of the new phosphines towards Cu^I, Au^I, and Pd^II metal centers has been explored, and a convenient procedure to introduce the most basic phosphine into metal complexes starting from air-stable phosphonium salt is described.     

Single-Molecule Magnets DyM2N@C80 and Dy2MN@C80 (M=Sc,Lu): The Impact of Diamagnetic Metals on Dy3+ Magnetic Anisotropy,Dy⋅⋅⋅Dy Coupling,and Mixing of Molecular and Lattice Vibrations

The substitution of scandium in fullerene single-molecule magnets (SMMs) DySc₂N@C₈₀ and Dy₂ScN@C₈₀ by lutetium has been studied to explore the influence of the diamagnetic metal on the SMM performance of dysprosium nitride clusterfullerenes. The use of lutetium led to an improved SMM performance of DyLu₂N@C₈₀, which shows a higher blocking temperature of magnetization (T_B=9.5 K), longer relaxation times, and broader hysteresis than DySc₂N@C₈₀ (T_B=6.9 K). At the same time, Dy₂LuN@C₈₀ was found to have a similar blocking temperature of magnetization to Dy₂ScN@C₈₀ (T_B=8 K), but substantially different interactions between the magnetic moments of the dysprosium ions in the Dy₂MN clusters. Surprisingly, although the intramolecular dipolar interactions in Dy₂LuN@C₈₀ and Dy₂ScN@C₈₀ are of similar strength, the exchange interactions in Dy₂LuN@C₈₀ are close to zero. Analysis of the low-frequency molecular and lattice vibrations showed strong mixing of the lattice modes and endohedral cluster librations in k-space. This mixing simplifies the spin–lattice relaxation by conserving the momentum during the spin flip and helping to distribute the moment and energy further into the lattice.