Self-assembly of a metal-organic cage-like structure bearing cofacial redox-active bis-(-semiquinone) copper(II) units.

Ditopic di--quinone with a resorcinol bridge exhibits the ability to self-assemble in a reaction with copper, giving a cage-like binuclear complex that, due to the cofacially placed metal ions, is capable of encapsulation of different solvent molecules as guest ligands. Notably, the geometry of the internal cavity of this complex adjusts depending on the coordinating properties of the encapsulated molecule (mono- or bidentate). A feature of this species is that the cage-forming units are copper(II) bis-semiquinonate moieties, capable of undergoing ligand-centered redox transformations.

Annulation of a 1,3-dithiole ring to a sterically hindered -quinone core. Novel ditopic redox-active ligands.

The fused 1,3-dithiole spacer seems to be very suitable for the functionalization of sterically hindered -quinones with additional groups capable of coordination of metal ions and/or possessing a redox activity. An effective method for the synthesis of sterically hindered -quinones containing 1,3-diketonate, dinitrile and -quinone-methide functional groups at the periphery of the ligand has been developed. The novel compounds have rigid and conjugated structures and exhibit properties typical of -quinones.

Redox-Modulations of Photophysical and Single-molecule Magnet Properties in Ytterbium Complexes Involving Extended-TTF Triads.

The reaction between the 2,2'-benzene-1,4-diylbis(6-hydroxy-4,7-di--butyl-1,3-benzodithiol-2-ylium-5-olate triad () and the metallo-precursor [Yb(hfac)]2HO led to the formation of a dinuclear coordination complex of formula [Yb(hfac)()]0.5CHCl (). After chemical oxidation of in 2,2'-cyclohexa-2,5-diene-1,4-diylidenebis(4,7-di--butyl-1,3-benzodithiole-5,6-dione (), the latter triad reacted with the [Yb(hfac)]2HO precursor to give the dinuclear complex of formula [Yb(hfac)()] ().

Regioisomerism in coordination chemistry: oxidative addition of a bifunctional ligand to palladium, stabilized with 1,2-bis(diphenylphosphino)ethane.

A unique phenomenon of regioisomerism in coordination chemistry was discovered: the reaction of a sterically hindered o-quinone annelated with a dithiete ring with Pddba in the presence of 1,2-bis(diphenylphosphino)ethane (dppe) gave a mixture of two regioisomers: catecholate 3Cat and dithiolate 3Dit. Both isomers were isolated in crystalline form and characterized by NMR, IR and X-ray diffractometry studies. DFT calculations reveal that the 3Dit species is more thermodynamically stable than the isomer 3Cat.

Protonated paramagnetic redox forms of di--quinone bridged with -phenylene-extended TTF: A EPR spectroscopy study.

The chemical oxidation and reduction processes of deprotonated, direduced -quinone-exTTF--quinone in protic solvents were studied by EPR spectroscopy. The formation of relatively stable paramagnetic protonated redox forms of the parent triad was very surprising. The character of spin-density distribution in the semiquinone-quinone and semiquinone-catechol redox forms indicates that the -phenylene-extended tetrathiafulvalene connector provides a quite effective electronic communication channel between dioxolene coordination sites.

New sterically-hindered o-quinones annelated with metal-dithiolates: regiospecificity in oxidative addition reactions of a bifacial ligand to the Pd and Pt complexes.

An unusual reactivity of sterically hindered o-quinones with an annelated dithiete ring towards coordination at a dithiolene site has been discovered. New Pd and Pt dithiolate complexes have been synthesized. The reaction proceeds regioselectively, and the quinone site of the parent ligand is not affected even while using an excess of the metal complex.

Sterically hindered o-quinone annulated with dithiete: a molecule comprising diolate and dithiolate coordination sites.

A new stable sterically hindered o-quinone annelated with a 1,2-dithiete ring was prepared by using mild conditions. The skeleton of the compound comprises diolate and dithiolate functions that have the potential to bind metals leading to the corresponding complexes. The reactivity of this compound as a ligand with respect to both coordination sites was studied.

A single molecule magnet behaviour in a D3h symmetry Dy(III) complex involving a quinone-tetrathiafulvalene-quinone bridge.

A Dy(III)-based dinuclear complex was synthesised and characterised by X-ray diffraction on single crystal and magnetic investigations. Dynamic magnetic measurements reveal a single molecule magnet behaviour for 1 which can be described as two single-ion magnets in a D(3h) local symmetry bridged by an acceptor-donor-acceptor ligand.