Twin hydrogen bonds with phosphine oxides: anticooperativity effects caused by competing proton donors

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2024-12-09 DOI:10.1039/d4cp04041d

Mikhail A. Kostin, Omar Alkhuder, Ruslan Asfin, Peter Tolstoy

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引用次数: 0

Abstract

In this computational work we study complexes with two equivalent intermolecular hydrogen bonds formed between Me₃PO and two identical proton donors (“twin” hydrogen bonds) for the set of 70 proton donor molecules. The changes of phosphorus chemical shift and vibrational frequency of P=O group upon complexation correlate quite good with the total strength of two hydrogen bonds. The set of explicit numerical dependences is proposed for assessing interatomic distances and hydrogen bond strengths from spectral data. Comparison with the results obtained for analogous previously studied 1:1 complexes allowed us to analyze in detail anticooperativity effects on the geometry, energy and spectral parameters. Two hydrogen bonds compete for PO acceptor group and their mutual weakening increases nonlinearly with strengthening of the complex, reaching approximately 25% in energy (which corresponds to 0.1 Å lengthening for short strong H-bonds), which is clearly seen in NMR and IR spectra and correlates well with the changes of the spectral parameters.

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.