Dušan P. Malenov*, Jelena M. Živković, Dubravka Z. Vojislavljević-Vasilev, Maria Andrea Mroginski and Snežana D. Zarić*,
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引用次数: 0
Abstract
In an attempt to reveal the hydrogen bond-accepting abilities of coordinated water, a survey of Cambridge Structural Database crystal structures yielded 1229 hydrogen bonds between free water as a hydrogen bond donor and coordinated water as a hydrogen bond acceptor. These hydrogen bonds can be divided into two major groups: short linear and long nonlinear hydrogen bonds, the former being more frequent. It was revealed that the short linear hydrogen bonds of acceptor-coordinated water are longer than the hydrogen bonds of donor-coordinated water, which suggests that they are weaker. DFT calculations at the B97D/def2-TZVP level demonstrated that these interactions usually do not surpass the energy of the hydrogen bond between free water molecules (−5.02 kcal/mol) since electrostatic potentials on coordinated water oxygen are less negative than the one on free water oxygen. However, if hydrogen bonds of acceptor-coordinated water are accompanied by substantial secondary interactions, then the interaction can be stronger. The strongest calculated interaction involving a neutral transition metal complex has the energy of −9.31 kcal/mol; these interactions become stronger if complexes are negatively charged, reaching the energy of −13.19 kcal/mol. Long nonlinear hydrogen bonds of acceptor-coordinated water appear only as additional interactions to other hydrogen bonds (short and linear). This study shows that hydrogen bonds of acceptor-coordinated water are abundant in crystal structures and can provide significant stabilization to supramolecular systems with metal complexes, despite them being weaker than hydrogen bonds of donor-coordinated water.
期刊介绍:
The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials.
Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.