Combination of Phenylsilsesquioxane and Acetate Ligands as an Approach to a Record High Nuclear CuNa-Cage. Synthesis, Unique Structure, and Catalytic Activity.

Self-assembly synthesis of mixed-ligand (silsesquioxane/acetate) complex allows to isolate record high nuclear copper(II) Cu-cage (1). In the presence of two additional sodium ions, a unique molecular architecture, with triple combination of ligands (cyclic and acyclic silsesquioxanes as well as acetates), has been formed. The structure was established by single-crystal X-ray diffraction based on the use of synchrotron radiation.

Highly Porous Scandium(III) Tetrafluoroisophthalate Framework for Adsorptive Separation of Light Alkanes.

The separation of light alkanes is one of the most important tasks for modern industry due to the widespread use of ethane and propane as chemical feedstocks. Their extraction from natural gas is a challenging task and is now carried out by cryogenic distillation at a limited number of plants around the world. The development of new materials for adsorption separation is therefore important.

An octanuclear 3-phenyl-5-(2-pyridyl)pyrazolate/phenylsilsesquioxane complex: synthesis, unique structure, and catalytic activity.

The first metallasilsesquioxane bearing pyrazolylpyridine ligands, the Cu-based complex 1, adopts a cage-like structure with two zigzag-type copper tetramers sandwiched by two cyclic Si silsesquioxane ligands. The four 3-phenyl-5-(2-pyridyl)pyrazolate ligands in 1 exhibit dual (chelating and bridging) modes of ligation. Compound 1 is very active in the oxidation of alkanes and alcohols.

Rational (supra)molecular design and catalytic activity of cage-like Cu-based phenylsilsesquioxanes.

An extended (, 19 distinct species) family of cage-like Cu-phenylsilsesquioxanes allowed us to accentuate the general regularities behind their structural organization. Influencing factors, namely the (i) size of external alkali metal ions (from Li to Cs) and (ii) nature of bridging linkers (including the smallest possible ones, like a water molecule) on the self-assembly/supramolecular assembly of such Cu-building blocks have been thoroughly explored. A CuK-based complex has been evaluated as a precatalyst in the oxidation of alkanes (cyclohexane, -heptane, methylcyclohexane) and alcohols.

Toward New Horizons in Verdazyl-Nitroxide High-Spin Systems: Thermally Robust Tetraradical with Quintet Ground State.

High-spin organic tetraradicals with significant intramolecular exchange interactions have high potential for advanced technological applications and fundamental research, but examples reported to date exhibit limited stability and processability. In this work, we designed the first tetraradical based on an oxoverdazyl core and nitronyl nitroxide radicals and successfully synthesized it using a palladium-catalyzed cross-coupling reaction of an oxoverdazyl radical bearing three iodo-phenylene moieties with a gold(I) nitronyl nitroxide-2-ide complex in the presence of a recently developed efficient catalytic system. The molecular and crystal structures of the tetraradical were confirmed by single crystal X-ray diffraction analysis.