Matrix isolation studies of hydrogen bonding. Vibrational correlation diagram
01 Mar 1975-The Journal of Physical Chemistry (American Chemical Society)-Vol. 79, Iss: 6, pp 615-620
About: This article is published in The Journal of Physical Chemistry.The article was published on 1975-03-01. It has received 114 citations till now. The article focuses on the topics: Halogen bond & Matrix isolation.
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TL;DR: The results attest that the pK(a) slide rule provides a reliable solution for the long-standing problem of H-bond-strength prediction and represents an efficient and practical tool for making such predictions directly accessible to all scientists.
Abstract: Unlike normal chemical bonds, hydrogen bonds (H-bonds) characteristically feature binding energies and contact distances that do not simply depend on the donor (D) and acceptor (:A) nature. Instead, their chemical context can lead to large variations even for a same donor−acceptor couple. As a striking example, the weak HO−H···OH2 bond in neutral water changes, in acidic or basic medium, to the 6-fold stronger and 15% shorter [H2O···H···OH2]+ or [HO···H···OH]− bonds. This surprising behavior, sometimes called the H-bond puzzle, practically prevents prediction of H-bond strengths from the properties of the interacting molecules. Explaining this puzzle has been the main research interest of our laboratory in the last 20 years. Our first contribution was the proposal of RAHB (resonance-assisted H-bond), a new type of strong H-bond where donor and acceptor are linked by a short π-conjugated fragment. The RAHB discovery prompted new studies on strong H-bonds, finally leading to a general H-bond classification ...
596 citations
TL;DR: The Electrostatic-Covalent H-Bond Model (ECHBM) as mentioned in this paper is derived from the systematic analysis of structural and spectroscopic data of a large number of O-H⋯O H-bonds.
594 citations
TL;DR: H-bond plays a double role in biological systems: on one hand, as a relatively strong directional interaction, it leads to relatively stable supramolecular structures, and on the other hand, because of dynamic features of the proton, it is an active site for initiation of chemical reactions.
Abstract: Among many various kinds of molecular interactions, the H-bond has a special position. The term is ubiquitous in the world that surrounds us, but also it is often applied in different ways. The H-bond is of great importance in natural sciences. This relates particularly to biological aspects, such as molecular recognition that could be a basis for the creation of life,1-4 formation of higher order structures of peptides and nucleic acids,5 and biochemical processes, particularly the enzymes catalyzed.6,7 One can say that the H-bond plays a double role in biological systems: on one hand, as a relatively strong directional interaction, it leads to relatively stable supramolecular structures, and on the other hand, because of dynamic features of the proton, it is an active site for initiation of chemical reactions. H-bonds are the source of specific properties of associated liquids, with water being the most popular among them.8 Water as a medium in which life was most probably created is saturated by H-bonds with highly mobile protons in between, even in the solid state.9 In many crystal lattices of organic compounds, the H-bonds are a decisive factor governing packing.10 In designing new interesting crystal structures, which is the subject of fast developing crystal engineer* To whom correspondence should be addressed. E-mail: slagra@ uni.lodz.pl or slagra@ccmsi.us. Fax: +48-42-6790447. 3513 Chem. Rev. 2005, 105, 3513−3560
583 citations
TL;DR: Recent advances in gas-phase ion spectroscopy are exploited to identify sharp spectral features that can be assigned to both the shared proton and the two tethered molecules in a survey of 18 cold, isolated [A·H+·B] ions, facilitating analysis of its properties within the context of a floppy polyatomic molecule.
Abstract: A proton shared between two closed-shell molecules, [A·H + ·B], constitutes a ubiquitous soft binding motif in biological processes. The vibrational transitions associated with the shared proton, which provide a direct probe of this interaction, have been extensively studied in the condensed phase but have yielded only limited detailed information because of their diffuse character. We exploited recent advances in gas-phase ion spectroscopy to identify sharp spectral features that can be assigned to both the shared proton and the two tethered molecules in a survey of 18 cold, isolated [A·H + ·B] ions. These data yield a picture of the intermolecular proton bond at a microscopic scale, facilitating analysis of its properties within the context of a floppy polyatomic molecule.
243 citations
TL;DR: Spectroscopic studies of base-hydrogen halide complexes are reviewed in this paper, including previously unpublished data for complexes of hydrogen chloride and hydrogen bromide with a variety of bases in argon matrices.
171 citations