Montero-Campillo M Merced, Alkorta Ibon, Elguero José
Departamento de Química, Módulo 13, Facultad de Ciencias and Institute of Advanced Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Campus de Excelencia UAM-CSIC, Cantoblanco, E-28049, Madrid, Spain.
Instituto de Química Médica, CSIC, Juan de la Cierva, 3, E-28006, Madrid, Spain.
Chemphyschem. 2018 Oct 5;19(19):2486-2491. doi: 10.1002/cphc.201800518. Epub 2018 Jul 19.
A series of A⋅water, B⋅water complexes (A=acid, B=base) are studied at the G4 level of theory to show that water acidity or basicity can be modulated by non-covalent interactions. Protic and non-protic acids interacting with water form hydrogen bonds or other kinds of non-covalent interactions, respectively, that may dramatically change the acidity of water up to almost 360 kJ ⋅ mol in terms of enthalpy. Similarly, hydrogen bonds responsible for the interaction between typical small nitrogen-containing Lewis bases and water can enhance the proton affinity of water by almost 300 kJ ⋅ mol . Our results reveal that these large enhancements are linearly related with the binding energy of the charged complexes, and are determined by the Lewis acid-base properties of the molecule involved in the interaction, allowing a quite precise modulation of the corresponding acid-base properties of water.
在G4理论水平下研究了一系列A⋅水、B⋅水络合物（A = 酸，B = 碱），结果表明水的酸度或碱度可通过非共价相互作用进行调节。质子酸和非质子酸与水相互作用时分别形成氢键或其他类型的非共价相互作用，这可能会使水合氢离子的酸度在焓方面显著变化，变化幅度高达近360 kJ·mol⁻¹。同样，负责典型的含氮小路易斯碱与水之间相互作用的氢键可使水的质子亲和能提高近300 kJ·mol⁻¹。我们的研究结果表明，这些大幅增强与带电络合物的结合能呈线性相关，并且由相互作用中所涉及分子的路易斯酸碱性质决定，从而能够相当精确地调节水相应的酸碱性质。
