Fe(III)-Based Phenylsilsesquioxane/Acetylacetonate Complexes: Synthesis, Cage-like Structure, and High Catalytic Activity.

Unprecedented iron-based silsesquioxane/acetylacetonate complexes were synthesized. The intriguing cage-like structure of compounds is alkaline metal-dependent: the FeLi complex includes condensed Si-silsesquioxane and four acetylacetonate ligands; the FeNa complex exhibits two cyclic Si-silsesquioxane and eight acetylacetonate ligands, while the FeK complex features two cyclic Si-silsesquioxane and six acetylacetonate ligands. The latter case is the very first observation of small trimeric silsesquioxane ligands in the composition of cage-like metallasilsesquioxanes.

Halogen Bonding in the Decoration of Secondary Coordination Sphere of Zinc(II) and Cadmium(II) Complexes: Catalytic Application in Cycloaddition Reaction of CO with Epoxides.

Three new zinc(II) complexes [Zn(HL)(HO)] (), [Zn(HL)(HO)] () (HL = 2,4-diiodo-5-(2-(2,4,6-trioxotetrahydropyrimidin-5(2)-ylidene)hydrazineyl)isophthalate) and [Zn(HL)(DMF)(HO)] () were synthesized by the reaction of Zn(II) salts with 5-(2-(2,4-dioxopentan-3-ylidene)hydrazineyl) isophthalic acid (HL), 2,4,6-triiodo-5-(2-(2,4,6-trioxotetrahydropyrimidin-5(2)-ylidene)hydrazineyl) isophthalic acid (HL) (in the presence of NHOH·HCl) and 5-(2-(2,4-dioxopentan-3-ylidene)hydrazineyl)-2,4,6-triiodoisophthalic acid (HL), respectively. According to the X-ray structural analysis, the intramolecular resonance-assisted hydrogen bond ring remains intact, with NO distances of 2.562(5) and 2.

A Family of Cagelike Mn-Silsesquioxane/Bathophenanthroline Complexes: Synthesis, Structure, and Catalytic and Antifungal Activity.

This study reports a novel family of cage manganesesilsesquioxanes prepared via complexation with bathophenanthroline (4,7-diphenyl-1,10-phenanthroline). The resulting Mn-, MnLi-, and MnNa-compounds exhibit several unprecedented cage metallasilsesquioxane structural features, including intriguing self-assembly of silsesquioxane ligands. Complexes were tested for fungicidal activity against seven classes of phytopathogenic fungi.

Synthesis and crystal structure of -poly[[[aqua-{2-[()-(1-cyano-2-imino-2-meth-oxy-ethyl-idene)hydrazin-yl]benzene-sulfonato}-sodium]-di-μ-aqua] dihydrate].

In the polymeric title compound, {[Na(CHNOS)(HO)]·2HO} , sixfold coordinated Na cations are linked into a chain parallel to [010] by sharing common water mol-ecules. Next to the four bridging water mol-ecules, each Na cation of the chain is bonded to the O atom of a terminal water mol-ecule and an O atom of the SO group of the sulfonate anion. Classical O-H⋯O, O-H⋯N and N-H⋯O hydrogen bonds and additional π-π inter-actions connect these chains into a three-dimensional network.

Chalcogen bonding in copper(II)-mediated synthesis.

The chalcogen bond (ChB) is a noncovalent attraction between an electrophilic chalcogen atom and a nucleophilic (Nu) region in the same (intramolecular) or another (intermolecular) molecular entity: R-Ch⋯Nu (Ch = O, S, Se or Te; R = substituents; Nu = nucleophile). ChB is comparable to the hydrogen and halogen bonds both in terms of strengths and directionality. However, in contrast to the monovalent halogen atoms, usually the divalent or tetravalent chalcogen atoms are able to display more than one electrophilic centre (on account of the existence of two or three species bonded to the chalcogen atom), which provides an additional opportunity in the use of this type of noncovalent binding in synthetic operations.

Halogen bonding in cadmium(II) MOFs: its influence on the structure and on the nitroaldol reaction in aqueous medium.

A solvothermal reaction of Cd(II) with the dicarboxyl-functionalized arylhydrazone pro-ligands, 5-(2-(2,4,6-trioxotetrahydro-pyrimidin-5(2)-ylidene)hydrazineyl)isophthalic acid (HL) and 5-(2-(2,4-dioxopentan-3-ylidene)hydrazineyl)isophthalic acid (HL), or their halogen bond donor centre(s) decorated analogs 2,4,6-triiodo-5-(2-(2,4,6-trioxotetrahydropyrimidin-5(2)-ylidene)hydrazineyl)isophthalic acid (HL) and 5-(2-(2,4-dioxopentan-3-ylidene)hydrazineyl)-2,4,6-triiodoisophthalic acid (HL), leads to the formation of known [Cd(HL)(HO)] (1) and new {[Cd(HL)(HO)(DMF)]·HO} (2), [Cd(HL)] (3) and {[Cd(μ-HO)(μ-HL)(HL)]·2HO} (4) coordination compounds, respectively. The aggregation of mononuclear units Cd-OC and Cd-OH coordination and C-I⋯I types of intramolecular halogen bonds lead to a dinuclear tecton 4. Both C-I⋯O and C-I⋯I types of intermolecular halogen bonds play a fundamental role in the supramolecular architectures of the obtained metal-organic frameworks 3 and 4.

Noncovalent Interactions at Lanthanide Complexes.

Lanthanide complexes have attracted a widespread attention due to their structural diversity, as well as multifunctional and tunable properties. The development of lanthanide based functional materials has often relied on the design of the secondary coordination sphere of the corresponding lanthanide complexes. For instance, usually simple lanthanide salts (solvento complexes) do not catalyze effectively organic reactions or provide low yield of the expected product, whereas the presence of a suitable organic ligand with a noncovalent bond donor or acceptor centre (secondary coordination sphere) modifies the symmetry around the metal centre in lanthanide complexes which then successfully can act as catalysts in both homogenous and heterogenous catalysis.