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The influence of adsorbed water on the dynamics of the organic linker 1,4-benzenedicarboxylate (BDC) in the metal organic framework NH 2 -MIL-125 was examined by applying  13 C Nuclear Magnetic Resonance (NMR) spectroscopy on samples loaded with different amounts of water. In particular, the analysis of (i) cross-polarization (CP)  13 C Magic Angle Spinning (MAS) NMR spectra in terms of chemical shift and line width of the carbon signals, (ii) variable contact time  13 C CP-MAS experiments, and (iii) longitudinal  13 C relaxation times indicated that, upon hydration, a dynamic process occurring on the microseconds timescale accelerates. This process could be identified with the rotation of the BDC benzene ring about its C 2  axis, with water competing with the carboxylic oxygen for hydrogen bonding with the aminic group. Other motions occurring at frequencies on the order of the  13 C Larmor frequency, i.e. 75 MHz, which contribute to the flexibility of the three-dimensional network, were detected, and identified with the twisting, libration and translation of the BDC linker.

Water Modulated Framework Flexibility in NH 2 -MIL-125: Highlights from 13 C Nuclear Magnetic Resonance