Solving the Hydrogen and Lithium Substructure of Poly(triazine imide)/LiCl Using NMR Crystallography |
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Authors: | Dr Maria B Mesch Kilian Bärwinkel Ya?ar Krysiak Dr Charlotte Martineau Prof?Dr Francis Taulelle Prof?Dr Reinhard B Neder Priv‐Doz?Dr Ute Kolb Prof?Dr Jürgen Senker |
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Institution: | 1. Inorganic Chemistry III, University of Bayreuth, Bayreuth, Germany;2. Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg University Mainz, Mainz, Germany;3. Tectospin, Institut Lavoisier de Versailles (ILV), UMR CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, Versailles cedex, France;4. Lehrstuhl für Kristallographie und Strukturphysik, Friedrich-Alexander-Universit?t Erlangen-Nürnberg, Erlangen, Germany |
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Abstract: | Poly(triazine imide) with incorporated lithium chloride has recently attracted substantial attention due to its photocatalytic activity for water splitting. However, an apparent H/Li disorder prevents the delineation of structure–property relationships, for example, with respect to band‐gap tuning. Herein, we show that through a combination of one‐ and two‐dimensional, multinuclear solid‐state NMR spectroscopy, chemical modelling, automated electron diffraction tomography, and an analysis based on X‐ray pair distribution functions, it is finally possible to resolve the H/Li substructure. In each cavity, one hydrogen atom is bound to a bridging nitrogen atom, while a second one protonates a triazine ring. The two lithium ions within each cavity are positioned between two nitrogen atoms of neighbouring triazine rings. The thereby induced local dipole moments cause slight buckling of the framework and lateral displacements of the Cl? ions at a coherence length below 2 nm. Nevertheless, the average structure conforms to space group P212121. In this way, we demonstrate that, in particular, the above‐mentioned techniques allow for smart interplay in delineating the real structure of PTI/LiCl. |
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Keywords: | electron diffraction NMR crystallography NMR spectroscopy poly(triazine imide) structure elucidation |
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