ABSTRACT
Ditopic di-o-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. Electrochemical and EPR spectroscopy studies showed that there is a channel for intramolecular electronic exchange interactions between the redox centres of the molecule.
ABSTRACT
Especially grown crystals (elongated plates) of the complex (1,10-phen)Co(3,6-DBSQ)2 (1) reversibly elastically bend under laser excitation (532 or 808 nm) and/or heating in the temperature interval â¼242-265 K (1,10-phen = 1,10-phenanthroline, 3,6-DBSQ = anion-radical and 3,6-DBCat = dianion of 3,6-di-tert-butyl-o-benzoquinone). The abrupt interconversion of valence tautomers is observed in this temperature range: (phen)Co(3,6-DBCat)(3,6-DBSQ) â (phen)Co(3,6-DBSQ)2. Solving the problem of design of photo- (thermo-) actuators with preset parameters, the series of solid solutions of general formula (phen)x(bpy)1-xCo(3,6-DBSQ)2 was obtained and crystallized as thin elongated plates. Crystals of each solid solution demonstrate the maximal photomechanical response (bending) at a temperature close to its own valence tautomeric (VT) transition temperature. On the other hand, the VT transition temperature depends on the composition of the solid solution. So, by setting the composition of the solid solution, one can set the temperature of the photomechanical response. It is the first example of temperature-manageable photomechanical properties.
ABSTRACT
A new bis(3,6-di-tert-butyl-catecholato)manganese complex with two 4-NIT-Py ligands was synthesized and characterized [4-NIT-Py = pyridine substituted at position 4 with nitronyl-nitroxide radical, 2-(pyridin-4-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl]. X-ray diffraction indicated an octahedral environment of the manganese atom with a trans arrangement of ligands. Bonds lengths in the inner coordination core of the metal and in the chelate cycles that are representative of the charge distribution between the metal and ligands displayed a Mn(IV)(Cat2-)2 charge distribution. Variable-temperature magnetic susceptibility measurements detected intramolecular ferromagnetic coupling between the Mn(IV) S = 3/2 spins and spins of nitronyl-nitroxyls and intermolecular ferromagnetic interactions of spins of adjacent nitronyl-nitroxide fragments in a chain of molecules at low temperatures. The last phenomenon is revealed by short contacts between nitronyl-nitroxide radicals of adjacent complex molecules.
ABSTRACT
A square-pyramidal mixed-halogen nickel(III) NCN-pincer complex (PipeNCN)NiClBr (where PipeNCN=2,6-bis(piperidinomethyl)phenyl) was structurally characterized. Bromine occupies apical position; pincer ligand and chlorine atom are in the basal plane. EPR detects that complex in solution exists as a mixture of two structural isomers with bromine or chlorine atoms in the top of pyramid.
Subject(s)
Algorithms , Halogens/chemistry , Magnetic Resonance Spectroscopy/methods , Models, Chemical , Models, Molecular , Nickel/chemistry , Computer Simulation , IsomerismABSTRACT
o-Semiquinonic nickel pincer complexes (R2PCP)Ni(SQ) show a versatile coordination sphere dynamics via "swing" or "fan" oscillations depending on the steric properties of the phosphorus substituents.
ABSTRACT
A number of square pyramidal o-semiquinonic nickel complexes with 2,6-bis(diphenylphosphinomethyl)phenyl were investigated by EPR spectroscopy in solution. The complexes have flexible coordination spheres and can exist in solution as two isomers rapidly (on the EPR timescale) interconverting one to another at room temperature. The equilibrium is entropy driven and does not significantly depend on the substituents in the semiquinone ring. The spin density distribution depends on mesomeric properties and bulkiness of substituents in ortho-position to oxygen atoms.
ABSTRACT
Square pyramidal o-semiquinonic nickel complexes with 2,6-bis(diphenylphosphinomethyl)phenyl have a flexible coordination sphere and exist in solution as the mixture of tautomers rapidly, according to EPR time scale, interconverting at room temperature.
