Composites of montmorillonite K10 (MMT K10) and ionic liquid (IL) containing a 1-butyl-3-methyl-imidazolium cation ([BMIm]⁺) and various anions, such as bis (trifluoromethylsulfonyl) imide ([NTf₂]⁻), trifluoromethanesulfonate ([OTf]⁻), and dicyanamide ([DCA]⁻) have been obtained in this work. A number of methods, such as dynamic light scattering (DLS), scanning electron microscopy (SEM), X-ray diffraction (XRD), thermal gravimetry (TG), differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and nitrogen adsorption–desorption have been used to characterize clay, and to study the structure and thermal behaviour of the composites. It has been found that the MMT K10 powder has a narrow particle size distribution with a peak at 246 nm and a mesoporous structure (S_BET=195 m²/g). According to the FTIR spectra, MMT K10/IL interaction depends on the IL type. It has been identified that confined ionic liquid interacts with both clay and adsorbed water in accordance with the hydrophilicity and size of the anion, in the following order: [DCA]⁻ > [OTf]⁻ > [NTf₂]⁻. Characteristic temperatures of glass transition, crystallization, and melting have been determined for the ionic liquids under study and their MMT K10 composites. It has been revealed that when IL is adsorbed on the surface of clay, the phase transitions in IL change. The greatest changes are observed in the case of BMImNTf₂. By applying the method of thermogravimetric analysis, it is shown that composite formation is accompanied by a decrease in the IL thermal stability. Apparently, the highly developed surface of montmorillonite K10, obtained by acid treatment, plays a major role in the decrease in the IL’s thermal stability. The influence of the IL anion on the thermal and spectral characteristics of an MMT K10/IL composite was studied for the first time.

The noncovalent interactions of (5,10,15,20-tetra(4-methylphenyl)porphinato)cobalt(II) (CoTTP) with C₆₀ and 1-N-methyl-2-(pyridin-4-yl)-3,4-fullero[60]pyrrolidine (PyC₆₀) were studied in toluene using absorption and fluorescence titration methods. The self-assembly in the 2:1 complexes (the triads) (C₆₀)₂CoTTP and (PyC₆₀)₂CoTTP was established. The bonding constants for (C₆₀)₂CoTTP and (PyC₆₀)₂CoTTP are defined to be (3.47 ± 0.69) × 10⁹ and (1.47 ± 0.28) × 10¹⁰ M⁻², respectively. ¹H NMR, IR spectroscopy, thermogravimetric analysis and cyclic voltammetry data have provided very good support in favor of efficient complex formation in the ground state between fullerenes and CoTTP. PyC₆₀/C₆₀ fluorescence quenching in the PyC₆₀/C₆₀–CoTTP systems was studied and the fluorescence lifetime with various CoTTP additions was determined. The singlet oxygen quantum yield was determined for PyC₆₀ and the intensity decrease in the ¹O₂ phosphorescence for C₆₀ and PyC₆₀ with the CoTTP addition leading to the low efficiency of intercombination conversion for the formation of the ³C₆₀* triplet excited state was found. Using femtosecond transient absorption measurements in toluene, the photoinduced electron transfer from the CoTTP in the excited singlet state to fullerene moiety was established. Quantum chemical calculations were used for the determination of molecular structure, stability and the HOMO/LUMO energy levels of the triads as well as to predict the localization of frontier orbitals in the triads.

Four types of ionic liquids (ILs) of [X]TFSI ([X]⁺ is a cation such as 1-butyl-3-methylimidazolium BMIm⁺, 1-butyl-1-methylpyrrolidinium BMPyrr⁺, 1-butyl-1-methylpiperidinium BMPip⁺ and methyltrioctylammonium MOc₃Am⁺ and TFSI⁻ is the bis(trifluoromethylsulfonyl)imide anion) were confined in halloysite nanoclay (Hal) at an excess ionic liquid concentration (IL : Hal ∼55 : 45 wt%) and studied by X-ray diffraction, TG, DSC analysis and FTIR spectroscopy. It was found that the physicochemical properties of ILs trapped by halloysite at maximum loading are similar to those of bulk ILs and change depending on the cation type and size. The cold crystallization temperature (T_cc) and melting point (T_m) of the crystalline mesophase in confined BMIm⁺ and BMPyrr⁺ ionic liquids are higher than in the bulk ones, while in the amorphous BMPyrr⁺ mesophase, the T_cc and T_m values decrease by 9.7 and 14.2 °C, respectively. Confined BMPip⁺ and MOc₃Am⁺ only have the glass transition temperature (T_g), which increases by 1.5 and 8.0 °C, respectively, compared to bulk ILs. The onset decomposition temperature (T_d) decreases by 106.5, 40.7, 19.0 and 7.7 °C in BMIm⁺, BMPip⁺, BMPyrr⁺ and MOc₃Am⁺, respectively. The changes in the properties are explained by the cation and anion interaction with halloysite, as well as by the transformation of the ionic liquid structure. It is found that in this case the amount of the TFSI⁻ anion trans-conformer increases in the following order: BMIm⁺ > BMPyrr⁺ ∼ BMPip⁺ >> MOc₃Am⁺.