NH Stretching Frequencies of Intramolecularly Hydrogen-Bonded Systems: An Experimental and Theoretical Study

The vibrational NH stretching transitions in secondary amines with intramolecular NH···O hydrogen bonds were investigated by experimental and theoretical methods, considering a large number of compounds and covering a wide range of stretching wavenumbers. The assignment of the NH stretching transitions in the experimental IR spectra was, in several instances, supported by measurement of the corresponding ND wavenumbers and by correlation with the observed NH proton chemical shifts. The observed wavenumbers were correlated with theoretical wavenumbers predicted with B3LYP density functional theory, using the basis sets 6-311++G(d,p) and 6-31G(d) and considering the harmonic as well as the anharmonic VPT2 approximation. Excellent correlations were established between observed wavenumbers and calculated harmonic values. However, the correlations were non-linear, in contrast to the results of previous investigations of the corresponding OH···O systems. The anharmonic VPT2 wavenumbers were found to be linearly related to the corresponding harmonic values. The results provide correlation equations for the prediction of NH stretching bands on the basis of standard B3LYP/6-311++G(d,p) and B3LYP/6-31G(d) harmonic analyses, with standard deviations close to 38 cm−1. This is significant because the full anharmonic VPT2 analysis tends to be impractical for large molecules, requiring orders of magnitude more computing time than the harmonic analysis.

Significance of nuclear quantum effects in hydrogen bonded molecular chains

In hydrogen bonded systems, nuclear quantum effects such as zero-point motion and tunneling can significantly affect their material properties through underlying physical and chemical processes. Presently, direct observation of the influence of nuclear quantum effects on the strength of hydrogen bonds with resulting structural and electronic implications remains elusive, leaving opportunities for deeper understanding to harness their fascinating properties. We studied hydrogen-bonded one-dimensional quinonediimine molecular networks which may adopt two isomeric electronic configurations via proton transfer. Herein, we demonstrate that concerted proton transfer promotes a delocalization of π-electrons along the molecular chain, which enhances the cohesive energy between molecular units, increasing the mechanical stability of the chain and giving rise to new electronic in-gap states localized at the ends. These findings demonstrate the identification of a new class of isomeric hydrogen bonded molecular systems where nuclear quantum effects play a dominant role in establishing their chemical and physical properties. We anticipate that this work will open new research directions towards the control of mechanical and electronic properties of low-dimensional molecular materials via concerted proton tunneling.

Concerning the selection of crystallization modifiers for non- hydrogen bonded systems: the case of benzophenone.

A design strategy for the selection of crystal growth modifiers for non-polar crystals is proposed and its application demonstrated for the case of benzophenone. The strongest intermolecular interaction in the...

Syntheses, structural characterization, and thermal behaviour of metal complexes with 3-aminopyridine as co-ligands

Six mixed metal complexes with 3-aminopyridine (3-ampy) as a co-ligand have been synthesized: catena-{[M(μ2-3-ampy)(H2O)4]SO4·H2O} (M=Ni (1) and Co (2)), [Co(3-ampy)4(NCS)2] (3), [Co(3-ampy)2(NCS)2] (4), [Co(3-ampy)4(N3)2] (5) and mer-[Co(3-ampy)3(N3)3] (6), (NCS−=isothiocyanate ion, N3− azide ion), and characterized by physio-chemical and spectroscopic methods as well as single crystal X-ray and powder diffraction. In the isostructural complexes 1 and 2 single μ2-3-ampy links the Ni(II) and Co(II) centers into polymeric chains. The mononuclear Co(II) and Co(III) pseudohalide complexes 3–6 reveal only terminal 3-ampy ligands. The 3-ampy ligands form supramolecular hydrogen bonded systems via their NH2-groups and non-covalent π-π ring-ring interactions via their pyridine moieties. Thermoanalytical properties were investigated for 1–3. Graphic abstract

Ultra-high piezoelectric coefficients and strain-sensitive curie temperature in hydrogen-bonded systems

We propose a new approach to obtain ultra-high piezoelectric coefficients that can be infinitely large theoretically, where ferroelectrics with strain-sensitive Curie temperature are necessary. We show the first-principles plus Monte Carlo simulation evidence that many hydrogen-bonded ferroelectrics (e.g. organic PhMDA) can be ideal candidates, which are also flexible and lead-free. Owing to the specific features of hydrogen bonding, their proton hopping barrier will drastically increase with prolonged proton transfer distance, while their hydrogen-bonded network can be easily compressed or stretched due to softness of hydrogen bonds. Their barriers as well as the Curie temperature can be approximately doubled upon a tensile strain as low as 2%. Their Curie temperature can be tuned exactly to room-temperature by fixing a strain in one direction, and in another direction, an unprecedented ultra-high piezoelectric coefficient of 2058 pC/N can be obtained. This value is even underestimated and can be greatly enhanced when applying a smaller strain. Aside from sensors, they can also be utilized for converting either mechanical or thermal energies into electrical energies due to high pyroelectric coefficients.

Combining Coordination and Hydrogen Bonds to Develop Discrete Supramolecular Metalla-Assemblies

In Nature, metal ions play critical roles at different levels, and they are often found in proteins. Therefore, metal ions are naturally incorporated in hydrogen-bonded systems. In addition, the combination of metal coordination and hydrogen bonds have been used extensively to develop supramolecular materials. However, despite this win-win combination between coordination and hydrogen bonds in many supramolecular systems, the same combination remains scarce in the field of coordination-driven self-assemblies. Indeed, as illustrated in this mini-review, only a few discrete supramolecular metalla-assemblies combining coordination and hydrogen bonds can be found in the literature, but that figure might change rapidly.