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The novel ruthenium octa-n-butoxy-naphthalocyanine complex was shown to retain an essentially monomeric state in dilute solutions. It was successfully applied as a homogeneous catalyst for carbene insertion into N–H bonds of amines with various substitution patterns, providing high yields of glycine derivatives. [ABSTRACT FROM AUTHOR]

Water-soluble porphyrins have garnered significant attention due to their broad range of applications in biomedicine, catalysis, and material chemistry. In this work, water-soluble platinum(II) and palladium(II) complexes with porphyrins bearing ethyl phosphonate substituents, namely, Pt/Pd 10-(ethoxyhydroxyphosphoryl)-5,15-di(p-carboxyphenyl)porphyrins (M3m, M = Pt(II), Pd(II)) and Pt/Pd 5,10-bis(ethoxyhydroxyphosphoryl)-10,20-diarylporphyrins (M1d–M3d; aryl = p-tolyl (1), mesityl (2), p-carboxyphenyl (3)), were synthesized by alkaline hydrolysis of the corresponding diethyl phosphonates M6m and M4d–M6d. NMR, UV–vis, and fluorescence spectroscopy revealed that the mono-phosphonates M3m tend to form aggregates in aqueous media, while the bis-phosphonates M3d exist predominantly as monomeric species across a wide range of concentrations (10−6–10−3 M), ionic strengths (0–0.81 M), and pH values (4–12). Single-crystal X-ray diffraction studies of the diethyl phosphonates Pt6d and Pd6d revealed that π–π stacking of the aromatic macrocycles is sterically hindered in the crystals, providing a rationale for the low degree of solution aggregation observed for ethyl phosphonate M3d. Photophysical studies of M3m and M1d–M3d demonstrated that these compounds are phosphorescent and generate singlet oxygen in aqueous solutions. Pd(II) complex Pd3d is an excellent photocatalyst for the oxidation of sulfides using di-oxygen in a solvent mixture (MeCN/H2O, 4 : 1 v/v). Under these conditions, various alkyl and aryl sulfides were quantitatively converted into the desired sulfoxides. For the oxygenation of mixed alkyl–aryl sulfides, Pd3d outperforms Pd(II) meso-tetrakis(p-carboxyphenyl)porphyrin (PdTCPP). This photocatalyst can be recycled and reused to afford sulfoxides with no loss of product yield. [ABSTRACT FROM AUTHOR]

Although the most promising applications of ionogels require their contact with aqueous media, few data are available on the stability of ionogels upon exposure to water. In this paper, a simple, easy-to-setup and precise method is presented, which was developed based on the continuous conductivity measurements of an aqueous phase, to study the washout of imidazolium ionic liquids (IL) from various silica-based ionogels immersed in water. The accuracy of the method was verified using HPLC, its reproducibility was confirmed, and its systematic errors were estimated. The experimental data show the rapid and almost complete (>90% in 5 h) washout of the hydrophilic IL (1-butyl-3-methylimidazolium dicyanamide) from the TMOS-derived silica ionogel. To lower the rate and degree of washout, several approaches were analysed, including decreasing IL content in ionogels, using ionogels in a monolithic form instead of a powder, constructing ionogels by gelation of silica in an ionic liquid, ageing ionogels after sol–gel synthesis and constructing ionogels from both hydrophobic IL and hydrophobic silica. All these approaches inhibited IL washout; the lowest level of washout achieved was ~14% in 24 h. Insights into the ionogels' structure and composition, using complementary methods (XRD, TGA, FTIR, SEM, NMR and nitrogen adsorption), revealed the washout mechanism, which was shown to be governed by three main processes: the diffusion of (1) IL and (2) water, and (3) IL dissolution in water. Washout was shown to follow pseudo-second-order kinetics, with the kinetic constants being in the range of 0.007–0.154 mol−1·s−1. [ABSTRACT FROM AUTHOR]

Phosphoryl podands of neutral type with a flexible ethylene glycol chain and diphenylphosphorylmethyl end groups are known for their complexation properties towards various cations. In this work, the complexation process between 1,3-bis(diphenylphosphoryl)-2-oxapropane (L) and lanthanide ions was studied. Namely, the stability constants of lanthanide complexes with L in acetonitrile were estimated by the method of spectrophotometric titration. It was found that the stability constants of Ln3+ complexes with L increase in the lanthanide series, which is consistent with the extraction and ion-selective properties of L. The extraction ability of L and this ligand in the presence of ionic liquids (ILs) such as methyltrioctylammonium nitrate (MTOAN) and bis[(trifluoromethyl)sulfonyl]imide 1-butyl-3-methylimidazolium (C4mimTf2N) was studied. It was found that in the presence of ILs, L extracts the elements of the yttrium subgroup of lanthanides much better than those of the cerium subgroup: SFLu/Ce(L–MTOAN) = 2.29; SFLu/Ce(L–C4mimTf2N) = 110.38. The use of the L–C4mimTf2N mixture in the processes of lanthanide separation into subgroups is much more efficient than the use of L without the addition of ILs or the use of the L–MTOAN mixture. The ion-selective properties of L towards Ln3+ ions were studied. Podand L exhibits potentiometric selectivity to Lu3+ ions. [ABSTRACT FROM AUTHOR]

Post-synthetic modification of proton-conducting metal–organic frameworks (MOFs) by loading small molecules capable of generating protons into pores is an efficient approach for developing a new type of material with improved ionic conductivity. Herein, the synthesis, characterization and proton conductivity of a novel electroneutral MOF based on palladium(II) meso-tetrakis(4-(phosphonatophenyl))porphyrinate, IPCE-1Pd, are reported. The exposure of the obtained framework to imidazole by the diffusion vapor method has surprisingly led to its complete crystal-to-crystal MOF-to-HOF transformation, resulting in the formation of a novel hydrogen-bonded organic framework (HOF) IPCE-1Pd_Im, which is the first example of such kind of structural change among all known MOFs. This modification has led to an almost 25-fold increase in the proton conductivity in comparison with the pristine MOF, reaching up to 6.54 × 10−3 S cm−1 at 85 °C and 95% relative humidity, which is one of the highest values among all known porphyrin-based HOFs. [ABSTRACT FROM AUTHOR]