RT Journal Article
T1 Dynamic Proton Bond: MH+·H2O ⇌ M·H3O+ Interconversion in Loosely Coordinated Environments
A1 Martínez-Haya, Bruno
A1 Avilés-Moreno, Juan Ramon
A1 Gámez, Francisco
A1 Martens, Jonathan
A1 Oomens, Jos
A1 Berden, Giel
K1 Proton bonding
K1 Supramolecular complexes
K1 Crown ethers
K1 Mass spectrometry
K1 Infrared ion spectroscopy
AB The interaction of organic molecules with oxonium cations within their solvation shell may lead to the emergence of dynamic supramolecular structures with recurrently changing host–guest chemical identity. We illustrate this phenomenon in benchmark proton-bonded complexes of water with polyether macrocyles. Despite the smaller proton affinity of water versus the ether group, water in fact retains the proton in the form of H3O+, with increasing stability as the coordination number increases. Hindrance in many-fold coordination induces dynamic reversible (ether)·H3O+ ⇌ (etherH+)·H2O interconversion. We perform infrared action ion spectroscopy over a broad spectral range to expose the vibrational signatures of the loose proton bonding in these systems. Remarkably, characteristic bands for the two limiting proton bonding configurations are observed in the experimental vibrational spectra, superimposed onto diffuse bands associated with proton delocalization. These features cannot be described by static equilibrium structures but are accurately modeled within the framework of ab initio molecular dynamics.
PB American Chemical Society
YR 2023
FD 2023-01-26
LK http://hdl.handle.net/10433/15788
UL http://hdl.handle.net/10433/15788
LA en
NO Journal of Physical Chemistry Letters 2023, 14, 1294−1300
NO Area of Physical Chemistry
DS RIO
RD May 22, 2026