Probing Interactions of N-Donor Molecules with Open Metal Sites within Paramagnetic Cr-MIL-101: A Solid-State NMR Spectroscopic and Density Functional Theory Study.

Understanding host-guest interactions is one of the key requirements for adjusting properties in metal-organic frameworks (MOFs). In particular, systems with coordinatively unsaturated Lewis acidic metal sites feature highly selective adsorption processes. This is attributed to strong interactions with Lewis basic guest molecules. Here we show that a combination of 13C MAS NMR spectroscopy with state-of-the-art density functional theory (DFT) calculations allows one to unravel the interactions of water, 2-aminopyridine, 3-aminopyridine, and diethylamine with the open metal sites in Cr-MIL-101. The 13C MAS NMR spectra, obtained with ultrafast magic-angle spinning, are well resolved, with resonances distributed over 1000 ppm. They present a clear signature for each guest at the open metal sites. Based on competition experiments this leads to the following binding preference: water < diethylamine ≈ 2-aminopyridine < 3-aminopyridine. Assignments were done by exploiting distance sum relations derived from spin-lattice relaxation data and 13C{1H} REDOR spectral editing. The experimental data were used to validate NMR shifts computed for the Cr-MIL-101 derivatives, which contain Cr3O clusters with magnetically coupled metal centers. While both approaches provide an unequivocal assignment and the arrangement of the guests at the open metal sites, the NMR data offer additional information about the guest and framework dynamics. We expect that our strategy has the potential for probing the binding situation of adsorbate mixtures at the open metal sites of MOFs in general and thus accesses the microscopic interaction mechanisms for this important material class, which is essential for deriving structure-property relationships.

Ab initio calculation of solid-state NMR spectra for different triazine and heptazine based structure proposals of g-C3N4.

We present a comprehensive theoretical study of the structure and NMR parameters of a large number of triazine and heptazine based structure proposals for g-C3N4 in different condensation states. This approach includes a detailed investigation of cyclic melon which tends toward the formation of densely packed hydrogen bonded meshes. In all of the investigated systems, we found planar layers to represent saddlepoints on the energy surface, whereas corrugated species were identified as minima. The corrugation source was linked to the repulsion of nitrogen lone pairs in close NN contacts. A linear dependency of the corrugation energy from the number of NN interactions in the investigated clusters was found. Heptazine based systems gain about twice as much energy per NN close contact in comparison to triazine structures which could be understood in terms of the distortion mechanism in the investigated structures. Furthermore, a full study of the 15N and 13C chemical shift tensors was performed for the different C/N layers. The description of the NMR parameters required dividing the investigated systems into subclusters for which the NMR tensors were calculated with density functional theory (DFT) methods. A statistical analysis of these entities allowed for the investigation of the change in the chemical shift upon corrugation and, in the case of the cyclic melon system, hydrogen bonding. With the here presented study, the most prominent structure models for g-C3N4 are characterized in terms of the 15N and 13C NMR parameters which now can directly be compared to experimental spectra.