Solving the Hydrogen and Lithium Substructure of Poly(triazine imide)/LiCl Using NMR Crystallography

Mesch MB, Baerwinkel K, Krysiak Y, Martineau C, Taulelle F, Neder R, Kolb U, Senker J (2016)

Publication Status: Published

Publication Type: Journal article

Publication year: 2016

Journal

Chemistry - A European Journal Wiley-VCH Verlag

Publisher: WILEY-V C H VERLAG GMBH

Book Volume: 22

Pages Range: 16876-16888

Journal Issue: 47

DOI: 10.1002/chem.201603726

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 bandgap 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 P2(1)2(1)2(1). In this way, we demonstrate that, in particular, the above-mentioned techniques allow for smart interplay in delineating the real structure of PTI/LiCl.

Authors with CRIS profile

Reinhard Neder Professur für Allgemeine Mineralogie/Kristallographie

Involved external institutions

Universität Bayreuth DE Germany (DE) Johannes Gutenberg-Universität Mainz (JGU) DE Germany (DE) Versailles Saint-Quentin-en-Yvelines University / Université de Versailles Saint-Quentin-en-Yvelines (UVSQ) FR France (FR)

How to cite

APA:

Mesch, M.B., Baerwinkel, K., Krysiak, Y., Martineau, C., Taulelle, F., Neder, R.,... Senker, J. (2016). Solving the Hydrogen and Lithium Substructure of Poly(triazine imide)/LiCl Using NMR Crystallography. Chemistry - A European Journal, 22(47), 16876-16888. https://doi.org/10.1002/chem.201603726

MLA:

Mesch, Maria B., et al. "Solving the Hydrogen and Lithium Substructure of Poly(triazine imide)/LiCl Using NMR Crystallography." Chemistry - A European Journal 22.47 (2016): 16876-16888.

BibTeX: Download