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Nuclear magnetic resonance spectroscopy (NMR) 1H, 35Cl, 27Al and 13C was applied to study underlying processes at the various stages of the synthesis of Au/Al nanoparticles. 35Cl spectrum was downfield shifted by 2.6 ppm as to the reference signal of the hydrated Cl− ion in NaCl solution. The evolution of the NMR spectra points to the formation of the stabilized shell around the gold containing nucleus. The shell restricts the supply of the reducing agents, which is the condition for the formation of Au2+ state at the concentration range in question. The electron paramagnetic resonance (EPR) spectra reveal formation of both Au2+ (g = 2.17) and Au+ (g < 2) intermediates incompletely reduced as well as Au0 clusters (g = 2.062) with odd number of atoms. The latter is coupled in many cases by the narrow signal with g = 2.0048 attributed to the radical in the supporting surrounding (tannin containing matrix in our case).

The general concepts are analyzed regarding the approach for the formation of paramagnetic species of noble metals, with a non-rigid (labile) molecule being used as a supporting matrix. The formation of the metal nanospecies follows three stages: (i) the metal ions are captured by the matrix, (ii) the reducing agent causes formation of individual atoms separated by the matrix fragments, (iii) the individual atoms agglomerate due to conformational transformations of the labile molecule-matrix. This algorithm is realized in two distinct systems: Ag-containing nanospecies embedded within the system of polyacrylic acid (PAA) chains grafted to the film of fluorinated ethylene propylene copolymer (FEP) and Au-containing nanospecies in the free matrix of tannin-citrate- oxo-hydroxo aluminate. The evolution of the electron paramagnetic resonance (EPR) spectra while cooling down demonstrates the appearance of the exchange interaction which is suppressed at higher temperatures by the vibrational modes of the molecule-matrix. The role of the oxo-hydroxo aluminate form is one of a molecular motor sorting the individual nanospecies by their size and charge state.

The structure and coordination environment of non-aqueous electrolytes based on bis(salicyl)borates of lithium, sodium, potassium, tetramethylammonium (MeBSB) and bis(oxalato)borates from lithium to cesium (MeBOB) using NMR spectroscopy have been investigated. Bis(salicyl)borates (BSB) and bis(oxalate)borates (BOB) of alkali metals and organic cations are considered as promising electroconductive components of electrolytes of modern chemical sources of current (lithium, sodium ion batteries and super-capacitors). The salts were synthesized by the microwave radiation method. The 13C and 11B NMR spectra analysis determined the presence of symmetric structure in BOB anion and the presence of two optical conformations of the BSB anion with labile coordination environment of boron. The conformations of the BSB are the result of the ion contact pairs formation. In the case of tetramethylammonium cation the presence of conformations are depended on the reactive medium. The conformational lability of the coordination sphere of NaBSB dissolved in DMAA is connected with increasing of the integral intensity of carboxyl group singles relatively signals of carbon atoms in fragments of another functional affiliation when the time delay between radio frequencies varies within 2-15 seconds. The difference in the structure of these anions leads to a change in the thermal dependence of the electrical conductivity of BSB and the transport of ions in non-aqueous solvents. Maximum electrical conductivity of salt solutions in DMFA is achieved at close concentrations of 0.75 m for KBSB and 0.77-1 m for NaBSB. The solubility of BSB is better than the BOB. Based on the measurements of the conductivity and the data of electrochemical impedance spectroscopy (the angle of inclination of spectra in the Nyquist coordinates in the low frequency range, the phase angle shift at a frequency) it was proposed the existence of two ways of ions and charge transfer in the electrolytes: diffusion and relay transport. The possibility of formation of a labile salt complex with a solvent due to hydrogen bonds is established.