A comprehensive study of the OH and OD stretching fundamentals in clusters methanol its isotopomers CH3OD, CD3OH, CD3OD provides detailed insights into hydrogen-bond mediated coupling as a function cluster size. The combination infrared Raman supersonic jet spectroscopy enables observation assignment all hydrogen-bonded modes isolated trimer tetramer. consistent explanation for spectral complexity observed more than decade ago terms low-frequency methyl umbrella motions is provided. Previous...

Acquiring spatial control of nanoscopic metal clusters is central to their function as efficient multi-electron catalysts. However, dispersing on surfaces or in porous hosts accompanied by an intrinsic heterogeneity that hampers detailed understanding the chemical structure and its relation reactivities. Tethering pre-assembled molecular into polymeric, crystalline 2D 3D networks constitutes unproven approach realizing ordered arrays chemically well-defined clusters. Herein, we report facile...

The highest frequency hydrogen bond fundamental of formic acid dimer, ν(24) (B(u)), is experimentally located at 264 cm(-1). FTIR spectra this in-plane bending mode (HCOOH)(2) and band centers its symmetric D isotopologues (isotopomers) recorded in a supersonic slit jet expansion are presented. Comparison to earlier studies room temperature reveals the large influence thermal excitation on maximum. Together with three B(u) combination states involving fundamentals recent progress for...

The vibrational dynamics of vacuum-isolated hydrogen-bonded complexes between water and the two simplest alcohols is characterized at low temperatures by Raman FTIR spectroscopy. Conformational preferences during adaptive aggregation, relative donor/acceptor strengths, weak secondary hydrogen bonding, tunneling processes in acceptor lone pair switching, thermodynamic anomalies are elucidated. ground state splitting methanol-water dimer predicted to be larger than 2.5 cm(-1). Two types...

The nitrosyl ligand exhibits interesting features for catalysis, such as strong π‑acidity and potential non‑innocent behavior. Pincer complexes are extraordinarily stable yet tunable often catalytically highly active. However, even though pincer could open new possibilities within, they have been scarcely explored within catalysis. Herein, we describe the synthesis of a novel family ruthenium PNP complex salts ([RuPNP(Cl)2NO]X) their use catalytic transfer hydrogenation. For hydrogenation...

A new Ru( ii )-complex with an amino-di(NHC) CNC pincer ligand was developed and characterised. In combination ionic liquid, it efficiently catalyses formic acid dehydrogenation under mild, additive-free conditions, producing H 2 CO .

The Ru-MACHO complex acts as a pre-catalyst for plethora of significant catalytic transformations. However, since its discovery approximately two decades ago, most enhancement attempts have been limited to varying the P-substituents increasing catalyst performance or replacing Ru greener alternatives. In this study we synthesize novel trans-L monohydrido iPrRu-MACHO derivatives that can act pre-catalysts operating under mild conditions while maintaining high activity and selectivity in...

In a recent theoretical investigation of DCl–H2O, HCl–D2O, and DCl–D2O [Felker et al., J. Phys. Chem. A, 125(29), 6437 (2021)] employing an accurate 9D permutation invariant polynomial-neural network potential energy surface highly efficient bound-state methodology, all the intramolecular vibrational eigenstates dimerization spectral shifts three isotopic binary 1:1 complexes have been predicted. By means dedicated annealing procedures, relative concentration dependencies, specialized dual...

The advancement of biorefinery technology for converting non‐edible biomass into bio‐based fuels and chemicals, like 5‐hydroxymethyl furfural (HMF), is attracting considerable attention as a sustainable substitute fossil‐based industrial chemicals. A highly selective, efficient, superior catalyst developed the aqueous‐phase hydrogenation 5‐hydroxymethylfurfural (HMF) to 2,5 dihydroxymethylfuran (DHMF) under very mild reaction conditions. Thus, at 30 °C with bar H2, 0.1 mol% novel cationic...

O-H bond stretching vibrations in hydrogen-bonded complexes embedded into cryogenic neon matrices are subtly downshifted from cold gas phase reference wavenumbers. To the extent that this shift is systematic, it enables as more universally applicable spectroscopic benchmark environments for quantum chemical predictions. Outliers indicative of either an assignment problem one two experiments or they reveal interesting dynamics structural effects on a function environment. We compile 6...

The effect of strong intermolecular hydrogen bonding on torsional degrees freedom is investigated by far-infrared absorption spectroscopy for different methanol dimer isotopologues isolated in supersonic jet expansions or embedded inert neon matrices at low temperatures. For the vacuum-isolated and Ne-embedded dimer, bond OH librational mode donor subunit finally observed ∼560 cm−1, blue-shifted more than 300 cm−1 relative to fundamental free monomer. acceptor ∼286 cm−1. experimental...

Terahertz absorption spectra have been recorded for the weakly bound CO2–H2O complex embedded in cryogenic neon matrices at 2.8 K. The three high-frequency van der Waals vibrational transitions associated with out-of-plane wagging, in-plane rocking, and torsional motion of isotopic H2O subunit assigned provide crucial observables benchmark theoretical descriptions this systems’ flat intermolecular potential energy surface. A (semi)-empirical value zero-point 273 ± 15 cm−1 from class...

The strong tendency for self-aggregation together with an intriguing mechanism the microhydration of monoethanolamine (MEA) have been explored by low-temperature far-infrared cluster spectroscopy in doped neon "quantum" matrices at 4 K complemented high-level quantum chemical modeling. In addition to assignment new mid-infrared perturbed intramolecular transitions, a distinct transition is unambiguously assigned concerted large-amplitude hydrogen bond librational motion MEA homodimer. This...

We demonstrate the facile vapor-phase synthesis of a novel, porous zero-valent metal–organic framework from reaction between volatile M(CO) 6 (M = Mo, W) and 4,4'-bipyridine precursors.

Intermolecular hydrogen bond libration modes of isolated cyclic methanol trimers (approximately 613 cm(-1)) and tetramers (695 760 are observed in pulsed jet Fourier transform infrared spectra found to exhibit sizeable anharmonicity mode coupling effects, opening the way for a microscopic interpretation broad librational bands alcohols. The correlation experimental OH stretching band intensities provides important constraints theoretical strengths, cluster densities, size assignments.

The intermolecular large-amplitude OH librational modes for mixed hydrogen-bonded complexes of water with methanol and t-butanol are unambiguously assigned the first time.

THz absorption spectra have been recorded for the weakly bound molecular complexes of H2O with C2H4 and C2H2 embedded in cryogenic neon matrices at 2.8 K. The observation assignment a large-amplitude acceptor OH librational mode C2H2—H2O complex 145.5 cm−1 confirms an intermolecular CH⋯O hydrogen-bonded configuration C2v symmetry subunit acting as hydrogen bond acceptor. two donor modes C2H4—H2O 255.0 187.5 cm−1, respectively, OH⋯π to π-cloud C2H4. A (semi)-empirical value change vibrational...

The self-association mechanisms of phenol have represented long-standing challenges to quantum chemical methodologies owing the competition between strongly directional intermolecular hydrogen bonding, weaker non-directional London dispersion forces and C-H⋯π interactions aromatic rings. present work explores these subtle relevance for biological molecular recognition processes via spectroscopic observations large-amplitude bond librational modes cluster molecules embedded in inert neon...

The true global potential energy minimum configuration of the formaldehyde dimer (CH2O)2, including presence a single or double weak intermolecular CH⋯O hydrogen bond motif, has been long-standing subject among both experimentalists and theoreticians as two different minima conformations Cs C2h symmetry have almost identical energies. present work demonstrates how class large-amplitude vibrational motion probed in THz region provides excellent direct spectroscopic observables for these...

Group 6 metal hexacarbonyl complexes are employed as building blocks for pyrazine-pillared metal–organic frameworks with zero-valent centres.

A combined microwave, infrared, and computational investigation of CHBrF(2) is reported. For the vibrational ground state, measurements in millimeter- sub-millimeter-wave regions for CH(79)BrF(2) CH(81)BrF(2) provided rotational centrifugal-distortion constants up to sextic terms as well hyperfine parameters (quadrupole-coupling spin-rotation interaction constants) bromine nucleus. The determination latter was made possible by recording spectra at sub-Doppler resolution, achieved means...

Intermolecular hydrogen bond librational modes in cyclic trimers and tetramers of methanol t-butyl alcohol isolated at low temperature pulsed supersonic jet expansions are observed by direct absorption spectroscopy the far-infrared region. The large amplitude probe strength directionality intermolecular bonds. In addition, their frequency intensity is very sensitive to angle which alkyl groups form with bonded ring. Theoretical predictions fail describe trends cluster size, alkylation...

FTIR spectra of the methanol dimer trapped in neon matrices are presented.

The self-assembly of lanthanide ions with ditopic organic spacers results in the formation complex tiling patterns that mimic structural motifs quasi-periodic 2D materials. linking trans-{LnI2}+ nodes (Ln = Gd, Dy) by both closed-shell and anion radicals 4,4′-bipyridine affords rare examples Archimedean tessellations a metal–organic framework. We furthermore demonstrate occurrence sizable magnetic exchange interactions slow relaxation magnetization behavior tessellation pattern....

This study investigates the potential of combining ε-polylysine and tannic acid to develop bio-based adhesives with enhanced water resistance. The two biomolecules exhibited complexation/precipitation in aqueous solutions pH range 5–9. Water-based were prepared using complexes formed at 5, 7, 9, followed by evaluation their adhesion properties both dry wet lap shear tests. higher values showed a larger strength improved To further enhance adhesive properties, an epoxide-based reagent was...