Binuclear Coordination Assemblies of Metal Tetraphenylporphyrins (M = Mn, Fe, and In) with Anionic Thioindigo Bridges as Promising Magnetic Systems with Tunable Properties.

A series of hybrids comprising two metal (Mn, Fe, and In) tetraphenylporphyrins axially substituted with anionic bidentate -thioindigo ligands (TI) were obtained. Substitution of the axial chloride anion by an oxygen atom of the dye forms short M-O bonds. Crystalline binuclear assemblies (TI)·{[MnTPP]·[MnTPP]}·CHCl ( = 2 for or 1 for ) and (TI){[MTPP]}·CHCl (M = Fe and = 2 for , M = In and = 1 for ) were synthesized.

Single-Ion Magnetism of the [Dy(hfac)] Anions in the Crystalline Semiconductor {TSeT}[Dy(hfac)] Containing Weakly Dimerized Stacks of Tetraselenatetracene.

The oxidation of tetraselenatetracene (TSeT) by tetracyanoquinodimethane in the presence of dysprosium(III) tris(hexafluoroacetylacetonate), Dy(hfac), produces black crystals of {TSeT}[Dy(hfac)] () salt, which combines conducting and magnetic sublattices. It contains one-dimensional stacks composed of partially oxidized TSeT molecules (formal averaged charge is +2/3). Dimers and monomers can be outlined within these stacks with charge and spin density redistribution.

Crystalline paramagnetic supramolecular 2D-polymer of the tetra(4-pyridyl)porphyrin and terbium(III) complex.

A new promising method for the preparation of crystalline 2D polymers based on tetra(4-pyridyl)porphyrin has been developed. Radical anion {HT(4-Py)P˙} species are used as the starting material. A new solid-state supramolecular array [{HT(4-Py)P}·{Tb(TMHD)}]·2.

Macrocycle- and metal-centered reduction of metal tetraphenylporphyrins where the metal is copper(II), nickel(II) and iron(II).

The reduction of metal(II) tetraphenylporphyrins, where metal(II) is copper, nickel or iron, has been performed in toluene solution in the presence of a cryptand. Cesium anthracenide was used as a reductant. Crystalline salts {cryptand(Cs)}{Cu(TPP)} (1) and {cryptand(Cs)}{Ni(TPP)}·CHCH (2) have been obtained.

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear MO Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet-Quartet Transitions in the Dianions.

Metal complexes of trithiadodecaazahexaphyrin (Hhp) that contain MO clusters inside a π-extended trianionic (Hhp) macrocycle have been prepared. Studies of the magnetic properties of NiO(Hhp) and CuO(Hhp) reveal a diamagnetic and EPR-silent trianionic (Hhp) macrocycle and diamagnetic Ni(O) or paramagnetic Cu(O) tetracations. The positive charge of MO(Hhp) is compensated by one acetate anion {MO(Hhp)}(CHCO).