A Dynamic Proton Bond: MH+?H2O? M?H3O+Interconversion in Loosely Coordinated Environments

被引:9
作者
Martinez-Haya, Bruno [1 ]
Aviles-Moreno, Juan Ramon [2 ]
Gamez, Francisco [3 ]
Martens, Jonathan [4 ]
Oomens, Jos [4 ]
Berden, Giel [4 ]
机构
[1] Univ Pablo de Olavide, Dept Phys Chem & Nat Syst, Seville 41013, Spain
[2] Univ Autonoma Madrid, Dept Appl Phys Chem, Madrid 28049, Spain
[3] Univ Complutense, Dept Quim Fis, Madrid 28040, Spain
[4] Radboud Univ Nijmegen, Inst Mol & Mat, FELIX Lab, NL-6525 ED Nijmegen, Netherlands
关键词
CROWN-ETHER COMPLEXES; GAS-PHASE BASICITIES; SMALL MOLECULES; HYDRONIUM ION; WATER; H3O+; SPECTROSCOPY;
D O I
10.1021/acs.jpclett.2c03832
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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)center dot H3O+ (etherH+)center dot 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.
引用
收藏
页码:1294 / 1300
页数:7
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