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The strong tendency for self-aggregation together with an intriguing mechanism for the microhydration of monoethanolamine (MEA) have been explored by low-temperature far-infrared cluster spectroscopy in doped neon "quantum" matrices at 4 K complemented by high-level quantum chemical modeling. In addition to the assignment of new mid-infrared perturbed intramolecular transitions, a distinct far-infrared transition is unambiguously assigned to the concerted large-amplitude hydrogen bond librational motion of the MEA homodimer. This observation confirms a global "head-to-head" intermolecular potential energy minimum associated with the formation of a compact doubly intermolecular OH⋯N hydrogen-bonded cyclic structure, where both monomeric intramolecular OH⋯N hydrogen bonds are broken upon complexation. By means of relative mixing ratio dependencies, dedicated annealing procedures, and selective complexation between MEA and isotopic H216O and H218O samples, distinct far-infrared transitions associated with large-amplitude intra-molecular hindered OH torsional motion and inter-molecular H2O librational (hindered c-type overall rotational) motion of the MEA monohydrate are furthermore assigned unambiguously for the first time. These spectroscopic observations reveal an intriguing metastable conformation, where H2O acts as a OH⋯O hydrogen bond donor to the hydroxy group instead of the amino group of MEA upon microhydration in the cryogenic neon environment, where the microhydration strengthens the intramolecular OH⋯N hydrogen bond of MEA due to hydrogen bond cooperativity., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

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 neon matrices as more universally applicable spectroscopic benchmark environments for quantum chemical predictions. Outliers are indicative of either an assignment problem in one of the two cryogenic experiments or they reveal interesting dynamics or structural effects on the complexes as a function of the environment. We compile 6 literature-known pairs of experimental data in jet and neon matrix expansions and realize a 6-fold expansion of that number through targeted matrix isolation and/or slit jet expansion spectroscopy presented in this work. In many cases, the neon matrix shift is less than the uncertainty of the currently best-performing blind quantum chemical predictions for the gas phase, but in specific cases, it may exceed the currently achievable theoretical accuracy. Some evidence for a positive correlation of the matrix shift with the hydrogen bond shift is found, similar to observations for helium nanodroplets. Outliers in particular for water acting as a donor are discussed, and in a few cases they call for a future reinvestigation. Substantial improvement in the correlation of the matrix shift with the hydrogen bond shift is achieved for ketone monohydrates by removing a vibrational resonance. New insights into nitrile hydration isomerism are obtained, and the linear OH stretching spectrum of the jet-cooled ammonia-water complex is presented for the first time. Vibrational spectroscopy in weakly perturbing solid rare gas quantum matrices for the benchmarking of gas phase theory and future explicit theoretical treatments of the quantum matrix environment to better understand the outliers are both encouraged.

The self-association mechanisms of phenol have represented long-standing challenges to quantum chemical methodologies owing to the competition between strongly directional intermolecular hydrogen bonding, weaker non-directional London dispersion forces and C-H⋯π interactions between the aromatic rings. The present work explores these subtle self-association mechanisms of relevance for biological molecular recognition processes via spectroscopic observations of large-amplitude hydrogen bond librational modes of phenol cluster molecules embedded in inert neon "quantum" matrices complemented by domain-based local pair natural orbital-coupled cluster DLPNO-CCSD(T) theory. The spectral signatures confirm a primarily intermolecular O-H⋯H hydrogen-bonded structure of the phenol dimer strengthened further by cooperative contributions from inter-ring London dispersion forces as supported by DLPNO-based local energy decomposition (LED) predictions. In the same way, the hydrogen bond librational bands observed for the trimeric cluster molecule confirm a pseudo- C 3 symmetric cyclic cooperative hydrogen-bonded barrel-like potential energy minimum structure. This structure is vastly different from the sterically favored "chair" conformations observed for aliphatic alcohol cluster molecules of the same size owing to the additional stabilizing London dispersion forces and C-H⋯π interactions between the aromatic rings. The hydrogen bond librational transition observed for the phenol monohydrate finally confirms that phenol acts as a hydrogen bond donor to water in contrast to the hydrogen bond acceptor role observed for aliphatic alcohols.

The specific far-infrared spectral signatures associated with highly localized large-amplitude out-of-plane librational motion of water molecules have recently been demonstrated to provide sensitive spectroscopic probes for the micro-solvation of organic molecules [Mihrin et al., Phys. Chem. Chem. Phys. 21(4), 1717 (2019)]. The present work employs this direct far-infrared spectroscopic approach to investigate the non-covalent intermolecular forces involved in the micro-solvation of a selection of seven ether molecules with systematically varied alkyl substituents: dimethyl ether, diethyl ether, diisopropyl ether, ethyl methyl ether, t-butyl methyl ether, and t-butyl ethyl ether. The ranking of the observed out-of-plane water librational band signatures for this selected series of ether-water complexes embedded in inert neon matrices at 4 K reveals information about the interplay of directional intermolecular hydrogen bond motifs and non-directional and long-range dispersion interactions for the micro-solvated structures. These far-infrared observables differentiate minor subtle effects introduced by specific alkyl substituents and serve as rigorous experimental benchmarks for modern quantum chemical methodologies of various levels of scalability, which often fail to accurately predict the structural variations and corresponding vibrational signatures of the closely related systems. The accurate interaction energies of the series of ether-water complexes have been predicted by the domain based local pair natural orbital coupled cluster theory with single-, double-, and perturbative triple excitations, followed by a local energy decomposition analysis of the energy components. In some cases, the secondary dispersion forces are in direct competition with the primary intermolecular hydrogen bonds as witnessed by the specific out-of-plane librational signatures.

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

The detailed chemical composition of crude oil in subsurface reservoirs provides important information about reservoir connectivity and can potentially play a very important role for the understanding of recovery processes. Relying on studying produced oil samples alone to understand the rock-fluid and fluid-fluid interactions is insufficient as the heavier polar components may be retained by tight reservoirs and not produced. These heavy and polar compounds that constitute the resin and asphaltene fractions of crude oil are typically present in low concentrations and yet are determining for the physical-chemical properties of the oil because of their polarity. In order to obtain a fingerprint analysis of oils including polar compounds from different wells, the oil content of drill cores has been extracted and analyzed. Infrared spectroscopy has been used to perform chemical fingerprinting of the oil extracted from drill cores sampled in different geographical locations of the Danish North Sea. Statistical analysis has been employed to identify the chemical differences within the sample set and explore the link between chemical composition and geographic location of the sample. A principal component analysis, based on spectral peak fitting in the 1800-1400 cm -1 range, has allowed for statistical grouping of the samples and identified the primary chemical feature characteristic of these groups. Statistically significant differences in the quantities of polar oxygen- and nitrogen-containing compounds were found between the oil wells. The results of this analysis have been used as guidelines and reference to establish an express statistical approach based on the full-range infrared spectra for a further expansion of the sample set. The chemical information presented in this work is discussed in relation to oil fingerprinting and geochemical analysis., Competing Interests: The authors declare no competing financial interest., (© 2020 The Authors. Published by American Chemical Society.)

β-Diketonates, such as acetylacetonate, are amongst the most common bidentate ligands towards elements across the entire periodic table and are considered wholly redox-inactive in their complexes. Herein we show that complexation of 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac - ) to Cr II spontaneously affords Cr III and a reduced β-diketonate radical ligand scaffold, as evidenced by crystallographic analysis, magnetic measurements, optical spectroscopy, reactivity studies, and DFT calculations. The possibility of harnessing β-diketonates as electron reservoirs opens up possibilities for new metal-ligand concerted reactivity in the ubiquitous β-diketonate coordination chemistry., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The high-resolution infrared absorption spectrum of the donor bending fundamental band ν 6 1 of the homodimer (HCN) 2 has been collected by long-path static gas-phase Fourier transform spectroscopy at 207 K employing the highly brilliant 2.75 GeV electron storage ring source at Synchrotron SOLEIL. The rovibrational structure of the ν 6 1 transition has the typical appearance of a perpendicular type band associated with a Σ-Π transition for a linear polyatomic molecule. The total number of 100 assigned transitions are fitted employing a standard semi-rigid linear molecule Hamiltonian, providing the band origin ν 0 of 779.05182(50) cm -1 together with spectroscopic parameters for the degenerate excited state. This band origin, blue-shifted by 67.15 cm -1 relative to the HCN monomer, provides the final significant contribution to the change of intra-molecular vibrational zero-point energy upon HCN dimerization. The combination with the vibrational zero-point energy contribution determined recently for the class of large-amplitude inter-molecular fundamental transitions then enables a complete determination of the total change of vibrational zero-point energy of 3.35±0.30 kJ mol -1 . The new spectroscopic findings together with previously reported benchmark CCSDT(Q)/CBS electronic energies [Hoobler et al. ChemPhysChem. 19, 3257-3265 (2018)] provide the best semi-experimental estimate of 16.48±0.30 kJ mol -1 for the dissociation energy D 0 of this prototypical homodimer., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The most prominent spectroscopic observable for the hydrogen bonding between individual molecules in liquid water is the broad absorption band detected in the spectral region between 300 and 900 cm-1. The present work demonstrates how the associated large-amplitude out-of-plane OH librational motion of H2O molecules also directly reflects the microsolvation of organic compounds. This highly localized OH librational motion of the first solvating H2O molecule causes a significant change of dipole moment and gives rise to a strong characteristic band in the far-infrared spectral region, which is correlated quantitatively with the complexation energy. The out-of-plane OH librational band origins ranging from 324.5 to 658.9 cm-1 have been assigned experimentally for a series of four binary hydrogen-bonded H2O complexes embedded in solid neon involving S-, O- and N-containing compounds with increasing hydrogen bond acceptor capability. The hydrogen bond energies for altogether eight binary H2O complexes relative to the experimental value of 13.2 ± 0.12 kJ mol-1 for the prototypical (H2O)2 system [Rocher-Casterline et al., J. Chem. Phys., 2011, 134, 211101] are revealed directly by these far-infrared spectroscopic observables. The far-infrared spectral signatures are able to capture even minor differences in the hydrogen bond acceptor capability of O atoms with slightly different alkyl substituents in the order H-O-C(CH3)3 > CH3-O-CH3 > H-O-CH(CH3)2 > H-O-CH2CH3.

The present work demonstrates that 99.9% enriched solid para-H2 below 3 K provides an excellent inert and transparent medium for the exploration of large-amplitude intermolecular vibrational motion of weakly bound van der Waals cluster molecules in the THz spectral region. THz absorption spectra have been generated for CO2/H2O and CS2/H2O mixtures embedded in enriched solid para-H2 and numerous observed transitions associated with large-amplitude librational motion of the weakly bound binary CO2H2O and CS2H2O van der Waals cluster molecules have been assigned together with tentative assignments for the ternary CS2(H2O)2 system. The interaction strength, directionality and anharmonicity of the weak van der Waals "bonds" between the molecules can be characterized via these THz spectral signatures and yield rigorous benchmarks for high-level ab initio methodologies. It is suggested that even a less stable linear conformation of the ternary CS2(H2O)2 system, where one H2O molecule is linked to each S atom of the CS2 subunit, may be formed due to the kinetics associated with the mobility of free H2O molecules in the soft para-H2 medium. In addition, the spectroscopic observations confirm a linear and planar global intermolecular potential energy minimum for the binary CS2H2O system with C2v symmetry, where the O atom on the H2O molecule is linked to one of the S atoms on the CS2 subunit. A semi-experimental value for the vibrational zero-point energy contribution of 1.93 ± 0.10 kJ mol-1 from the class of large-amplitude intermolecular vibrational modes is proposed. The combination with CCSD(T)/CBS electronic energy predictions provides a semi-experimental estimate of 5.08 ± 0.15 kJ mol-1 for the binding energy D0 of the CS2H2O van der Waals system.

The high-resolution terahertz absorption spectrum of the large-amplitude intermolecular donor librational band ν of the homodimer (HCN) 2 has been recorded by means of long-path static gas-phase Fourier transform spectroscopy at 207 K employing a highly brilliant electron storage ring source. The rovibrational structure of the ν band has the typical appearance of a perpendicular type band of a Σ-Π transition for a linear polyatomic molecule. The generated terahertz spectrum is analyzed employing a standard semi-rigid linear molecule Hamiltonian, yielding a band origin ν 0 of 119.11526(60) cm -1 together with values for the excited state rotational constant B', the excited state quartic centrifugal distortion constant D J ' and the l-type doubling constant q for the degenerate state associated with the ν mode. The until now missing donor librational band origin enables the determination of an accurate experimental value for the vibrational zero-point energy of 2.50 ± 0.05 kJ mol -1 arising from the entire class of large-amplitude intermolecular modes. The spectroscopic findings are complemented by CCSD(T)-F12b/aug-cc-pV5Z (electronic energies) and CCSD(T)-F12b/aug-cc-pVQZ (force fields) electronic structure calculations, providing a (semi)-experimental value of 17.20 ± 0.20 kJ mol -1 for the dissociation energy D 0 of this strictly linear weak intermolecular CHN hydrogen bond.

The true global potential energy minimum configuration of the formaldehyde dimer (CH 2 O) 2 , including the presence of a single or a double weak intermolecular CH⋯O hydrogen bond motif, has been a long-standing subject among both experimentalists and theoreticians as two different energy minima conformations of C s and C 2h symmetry have almost identical energies. The present work demonstrates how the class of large-amplitude hydrogen bond vibrational motion probed in the THz region provides excellent direct spectroscopic observables for these weak intermolecular CH⋯O hydrogen bond motifs. The combination of concentration dependency measurements, observed isotopic spectral shifts associated with H/D substitutions and dedicated annealing procedures, enables the unambiguous assignment of three large-amplitude infrared active hydrogen bond vibrational modes for the non-planar C s configuration of (CH 2 O) 2 embedded in cryogenic neon and enriched para-hydrogen matrices. A (semi)-empirical value for the change of vibrational zero-point energy of 5.5 ± 0.3 kJ mol -1 is proposed for the dimerization process. These THz spectroscopic observations are complemented by CCSD(T)-F12/aug-cc-pV5Z (electronic energies) and MP2/aug-cc-pVQZ (force fields) electronic structure calculations yielding a (semi)-empirical value of 13.7 ± 0.3 kJ mol -1 for the dissociation energy D 0 of this global potential energy minimum.