Ligand dynamics on the surface of zirconium oxo clusters

文献信息

发布日期 2009-03-26
DOI 10.1039/B820731C
影响因子 3.676
作者

Philip Walther, Michael Puchberger, F. Rene Kogler, Karlheinz Schwarz, Ulrich Schubert


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摘要

The dynamics of carboxylate ligands on the surface of zirconium oxo clusters was investigated in two case studies. Zr4O2(methacrylate)12 was investigated by one- and two dimensional NMR spectra both in the solid state and in solution. In solution, the cluster is C2h symmetric; stepwise intramolecular exchange of the four non-equivalent ligands was observed when the temperature was raised from −80 °C to −50 °C. The individual exchange processes were assigned to different ligand positions. Ab initio molecular dynamics simulations were performed for Zr6(OH)4O4(formate)12 to study the trajectory for the rearrangement of three chelating ligands into bridging positions, i.e. the conversion of the C3-symmetric into an Oh-symmetric cluster. The observation of a dip in the energy barrier along the reaction coordinate was related to the intermediate formation of hydrogen bonds between the moving oxygen atom of the rearranging ligand and a μ3-OH group of the cluster. Thus, the motion of the ligand requires a concerted motion in three dimensions.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

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.

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