The gem-diol moieties of organic compounds are rarely isolated or even studied in the solid state. Here, liquid- and solid-state NMR, together with single-crystal X-ray diffraction studies, were used to show different strategies to favor the gem-diol or carbonyl moieties and to isolate hemiacetal structures in formylpyridine and vitamin-B-related compounds. The change in position of the carbonyl group in pyridine compounds had a clear and direct effect on the hydration, which was enhanced by trifluoroacetic acid addition. Because of their biochemical importance, vitamin-B-related compounds were studied with emphasis on the elucidation of the gem-diol, cyclic hemiacetal or carbonyl structures that can be obtained in different experimental conditions. In particular, new racemic mixtures for the cyclic hemiacetal structure from pyridoxal are reported in trifluoroacetate and hydrochloride derivatives.

The stability of gem-diol forms in imidazolecarboxaldehyde isomers was studied by solid-state nuclear magnetic resonance (ss-NMR) combined with single-crystal X-ray diffraction studies. These methodologies also allowed determining the factors governing the occurrence of such rare functionalization in carbonyl moieties. Results indicated that the position of the carbonyl group is the main factor that governs the generation of geminal diols, having a clear and direct effect on hydration, since, under the same experimental conditions, only 36% of 5-imidazolecarboxaldehydes and 5% of 4-imidazolecarboxaldehydes were hydrated, as compared to 2-imidazolecarboxaldehydes, with which a 100% hydration was achieved. Not only did trifluoroacetic acid favor the addition of water to the carbonyl group but also it allowed obtaining single crystals. Single crystals of the gem-diol and the hemiacetal forms 2-imidazolecarboxaldehyde and N-methyl-2-imidazolecarboxaldehyde, respectively, were isolated and studied through H ss-NMR. Mass spectrometry and solution-state NMR experiments were also performed to study the hydration process.

The complex chemical functionalization of the aldehyde group was elucidated in copper and cobalt complexes for 4- and 3-pyridinecarboxaldehyde ligands.

Three new single-crystal structures were isolated for picolinic acid (2), the trifluoroacetate salt of picolinic acid (1), and pyridoxal hydrochloride (3). These compounds displayed unconventional crystallographic features that must be considered when structural refinements are carried out. Thus, the generated Fourier differences map obtained with the diffraction data collected at 100 K was crucial to visualize electron densities, which were balanced by either one hydrogen atom or a hydrogen atom with an occupancy factor of 1/2 located between either two carboxylate moieties, two phenolic oxygen atoms, or two pyridinic nitrogen atoms. Moreover, NMR studies were conducted to analyze the bulk chemical composition of single crystals of 2-pyridinecarboxylic acid obtained from the gem-diol/hemiacetal forms and the polymerization products after the treatment of 2-pyridinecarboxaldehyde with TFA:H2O (1) or a diluted Cu­(NO3)2 solution (2). The quantitative yield of the pyridoxal hydrochloride crystalline material (3) obtained from a diluted CuCl2 solution was exhaustively characterized by solid-state NMR methods. These methods allowed the resolution of the signals corresponding to the protons of the hydroxyl moiety of the intramolecular hemiacetal group and the phenolic hydrogen. Theoretical calculations using DFT methods were done to complement the atomic location of the hydrogen atoms obtained from the X-ray analysis.

This work describes the synthesis of 4-(4-AcPy) and 3-acetylpyridine (3-AcPy) copper soluble complexes for the activation of hydrogen peroxide and the concomitant generation of reactive oxygen species (ROS). Given the paramagnetic effects of copper ions in the Nuclear Magnetic Resonance (NMR) lines, we aimed at demonstrating that the combination of high-resolution 2D solid-state NMR experiments, Electron Paramagnetic Resonance (EPR), single-crystal X-ray crystallography and Density Func-tional Theory (DFT) calculations allows a detailed study of the chemical structure of the ligands and the surrounding metal ions. The copper complexes synthesized with CuCl 2 were useful for the activation of H 2 O 2 during which the only ROS was the hydroxyl one, as demonstrated by EPR experiments. A removal of methyl orange (MO) azo-dye higher than 85 % was achieved in 200 minutes, combining 1.7 mM of copper complexes with 60 mM of H 2 O 2 and 40 μM of MO.

Novel coordination compounds, mono‐ (1) and binuclear copper complexes (2) and a zinc complex (3) were synthesized and studied through single‐crystal X‐ray crystallography, solid‐state NMR and EPR techniques to determine the chemical functionalization of the carbonyl group in N‐methyl‐2‐imidazolecarboxaldehyde ligand. Particularly, molecules containing carbonyl groups are versatile ligands that give rise to a wide range of new materials due to the high reactivity of the carbonyl group. However, the chemical identification of the functional group present in these coordination compounds is a challenge because the copper ion affects the NMR signals. In this sense, X‐ray crystallography becomes an indispensable tool for the analysis. The imidazole ligands in copper complexes 1 and 2 were found to be the aldehyde and the gem‐diol forms, respectively. Furthermore, the gem‐diol and carboxylate moieties were detected in the crystal lattice for the zinc complex 3 and studied by solution‐ and solid‐state NMR.