RESUMEN
Convenient self-assembly synthesis of copper(II) complexes via double (phenylsilsesquioxane and acetate) ligation allows to isolate a family of impressive sandwich-like cage compounds. An intriguing feature of these complexes is the difference in the structure of a pair of silsesquioxane ligands despite identical (Cu6) nuclearity and number (four) of acetate fragments. Formation of particular combination of silsesquioxane ligands (cyclic/cyclic vs condensed/condensed vs cyclic/condensed) was found to be dependent on the synthesis/crystallization media. A combination of Si4-cyclic and Si6-condensed silsesquioxane ligands is a brand new feature of cage metallasilsesquioxanes. A representative Cu6-complex (4) (with cyclic silsesquioxanes) exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. Maximum yield of the products of cyclohexane oxidation attained 30 %. The compound 4 was also tested as catalyst in the Baeyer-Villiger oxidation of cyclohexanone by m-chloroperoxybenzoic acid: maximum yields of 88 % and 100 % of ϵ-caprolactone were achieved upon conventional heating at 50 °C for 4â h and MW irradiation at 70 or 80 °C during 30â min, respectively. It was also possible to obtain the lactone (up to 16 % yield) directly from the cyclohexane via a tandem oxidation/Baeyer-Villiger oxidation reaction using the same oxidant.
RESUMEN
A small family of nonanuclear Cu5Cs4-based phenylsilsesquioxanes 1-2 were prepared by a convenient self-assembly approach and characterized by X-ray diffraction studies. The compounds 1 and 2 show some unprecedented structural features such as the presence of a [Ph14Si14O28]14- silsesquioxane ligand and a CuII5CsI4 nuclearity in which the metal cations occupy unusual positions within the cluster. Copper ions are "wrapped" into a silsesquioxane matrix, while cesium ions are located in external positions. This resulted in cesium-involved aggregation of coordination polymer structures. Both compounds 1 and 2 realize specific metallocene (cesium-phenyl) linkage between neighboring cages. Compound 2 is evaluated as a catalyst in the Baeyer-Villiger (B-V) oxidation of cyclohexanone and tandem cyclohexane oxidation/B-V oxidation of cyclohexanone with m-chloroperoxybenzoic acid (mCPBA) as an oxidant, in an aqueous acetonitrile medium, and HNO3 as the promoter. A quantitative yield of ε-caprolactone was achieved under conventional heating at 50 °C for 4 h or MW irradiation for 30 min (for cyclohexanone as substrate); 17 and 19% yields of lactone upon MW irradiation at 80 °C for 30 min and heating at 50 °C for 4 h, respectively (for cyclohexane as a substrate), were achieved. Complex 2 was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with peroxides at 60 °C in acetonitrile. The maximum yield of cyclohexane oxidation products was 30%. Complex 2 exhibits high activity in the oxidation of alcohols.
RESUMEN
The synthesis, crystal structures and magnetic properties are reported for three novel mixed-valence tetranuclear [MnII2MnIII2(HBuDea)2(BuDea)2(EBA)4] (1), [MnII2MnIII2(HBuDea)2(BuDea)2(DMBA)4] (2) and undecanuclear [MnII3MnIII8O4(OH)2(BuDea)6(DMBA)8] (3) clusters, where H2BuDea is N-butyldiethanolamine, HEBA is 2-ethylbutyric acid and HDMBA is 2,2-dimethylbutyric acid. The compounds have been prepared through self-assembly reactions of manganese(ii) chloride with H2BuDea and respective carboxylic acid in methanol solution in air, affording 1 with HEBA, and 2 or 3 with HDMBA, depending on the experimental conditions. The single crystal X-ray analysis reveals that 1 and 2 have similar centrosymmetric structures based on the {M4(µ3-O)2(µ-O)4} core, while 3 discloses the unprecedented {M11(µ-O)4(µ3-O)12} one. The Mn4 complexes display single-molecule magnet (SMM) behavior with a S = 9 spin ground state and a high energy barrier Ueff/kB of up to 51 K. The magnetic properties of 2 are successfully modeled with JMnIII-MnIII/hc = 25.7 cm-1 and two JMnIII-MnII/hc constants of 3.1 and -0.93 cm-1 (data correspond to the H = -Js1·s2 formalism). The Mn11 cluster exhibits a paramagnetic behavior with dominant antiferromagnetic coupling. A possible influence of intermolecular effects and of different peripheries of the magnetic cores designed by using 2-ethylbutyrate (in 1) or 2,2-dimethylbutyrate (in 2) on the magnetic properties of 1 and 2 is discussed. The experimental magnetostructural correlations for the {MnII2MnIII2(µ3-O)2(µ-O)4} cores, supported by broken symmetry DFT calculations, disclose the X-MnIIIMnIII angle and MnIII-O distance (where MnIII-X and MnIII-O are axial Jahn-Teller bonds) as the structural factors having the strongest influence on JMnIII-MnIII exchange coupling. It is shown that two JMnIII-MnII constants are necessary for the correct description of magnetic exchange couplings in the {MnII2MnIII2(µ3-O)2(µ-O)4} tetranuclear unit.
RESUMEN
Three new 6-methyl-2-oxo-1,2-dihydroquinoline-3-carbaldehyde-thiosemicarbazones-N-4-substituted pro-ligands and their Cu(II) complexes (1, -NH2; 2, -NHMe; 3, -NHEt) have been prepared and characterized. In both the X-ray structures of 1 and 3, two crystallographically independent complex molecules were found that differ either in the nature of weakly metal-binding species (water in 1a and nitrate in 1b) or in the co-ligand (water in 3a and methanol in 3b). Electron Paramagnetic Resonance (EPR) measurements carried out on complexes 1 and 3 confirmed the presence of such different species in the solution. The electrochemical behavior of the pro-ligands and of the complexes was investigated, as well as their biological activity. Complexes 2 and 3 exhibited a high cytotoxicity against human tumor cells and 3D spheroids derived from solid tumors, related to the high cellular uptake. Complexes 2 and 3 also showed a high selectivity towards cancerous cell lines with respect to non-cancerous cell lines and were able to circumvent cisplatin resistance. Via the Transmission Electron Microscopy (TEM) imaging technique, preliminary insights into the biological activity of copper complexes were obtained.
