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.

Paramagnetic {[Fe(CO)]-μ-η:η-η:η-(C)} Dimer Bridged by Iron Atoms and C-C Bonds: Effect of Starting Iron Carbonyls on Structures and Properties of Negatively Charged Iron-Bridged Fullerene Dimers.

The reaction between an excess of Fe(CO) with {Cryptand(K)}(C) produced the salt {Cryptand(K)}{[Fe(CO)]-μ-η:η-η:η-(C)}·4CHCl () containing negatively charged iron-bridged fullerene dimers. In these dimers, the C cages are linked via two Fe(CO) fragments, forming short Fe-C(C) bonds with a length of 2.070(3) Å and via two intercage C-C bonds with a length of 1.

Bimetallic neutral and anionic complexes of transition metal (Co, Mn) carbonyls with indium(III) phthalocyanine.

Heterobimetallic {[Co(CO)][In(Pc)]} (1) and (Cp*Cr){[Mn(CO)][In(Pc˙)]}·2CHCl (2) complexes based on indium(III) phthalocyanine (Pc) were obtained as crystals. The complexes were synthesized by single (1) and double (2) reduction of indium(III) phthalocyanine chloride in the presence of transition metal carbonyls. Complex 1 contains dianionic Pc macrocycles.

Magnetic behavior and ground spin states for coordination {L·[M(Hal)]} assemblies (Hal = Cl or I) of radical trianion hexacyanohexaazatriphenylenes (L) with three coordinated high-spin Fe ( = 2) or Co ( = 3/2) centers.

A series of trianion assemblies of hexaazatriphenylenehexacarbonitrile {HAT(CN)} and hexaazatrinaphthylenehexacarbonitrile {HATNA(CN)} with three Fe(II) or Co(II) ions: {cryptand(K)}·{HATNA(CN)·(FeI)}·2CHCl (1), {cryptand(K)}·{HATNA(CN)·(CoI)}·2CHCl (2), and (CV)·{HAT(CN)·(CoCl)}·0.5(CVCl)·2.5CHCl (3) are synthesized (CVCl = crystal violet).

Negatively Charged Iron-Bridged Fullerene Dimer {Fe(CO)-μ-η,η-C}.

The interaction of {Cryptand(K)}(C) with Fe(CO) produced {Cryptand(K)}{Fe(CO)--,-C}·2.5CHCl () as the first negatively charged iron-bridged fullerene C dimer. The bridged iron atoms are coordinated to two 6-6 bonds of one C hexagon with short and long C(C)-Fe bonds with average lengths of 2.

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.

Trinuclear coordination assemblies of low-spin dicyano manganese(II) ( = 1/2) and iron(II) ( = 0) phthalocyanines with manganese(II) acetylacetonate, tris(cyclopentadienyl)gadolinium(III) and neodymium(III).

The reaction of MnPc, FePc or FePcCl with KCN in the presence of cryptand[2.2.2] yielded dicyano-complexes {cryptand(K)}{M(CN)(macrocycle)}·CHCl (M = Mn and Fe, = 1 and 2) that were used for the preparation of trinuclear assemblies of the general formula {cryptand(K)}{M(CN)Pc·(ML)}·CHCl (M = Mn and Fe; = 1, 4 and 5).

Complexes of transition metal carbonyl clusters with tin(II) phthalocyanine in neutral and radical anion states: methods of synthesis, structures and properties.

Coordination of tin(II) phthalocyanine to transition metal carbonyl clusters in neutral {Sn(Pc)} or radical anion {Sn(Pc˙)} states is reported. Direct interaction of Co(CO) with {Sn(Pc)} yields a crystalline complex {Co(CO)·Sn(Pc)} (1). There is no charge transfer from the cluster to phthalocyanine in 1, which preserves the diamagnetic Pc macrocycle.

Weak Antiferromagnetic Exchange and Ferromagnetic Alignment of Fe (S=2) Spins in Differently Charged {HAT ⋅ (Fe Cl ) } (n=2- and 3-) Assemblies of Hexaazatriphenylenes (HAT).

Hexaazatrianthracene (HATA) and hexaazatriphenylenehexacarbonitrile {HAT(CN) } are reduced by metallic iron in the presence of crystal violet (CV )(Cl ). Anionic ligands are produced, which simultaneously coordinate three Fe Cl to form (CV ) {HATA ⋅ (Fe Cl ) }  ⋅ 3 C H Cl (1) and (CV ) {HAT(CN) (Fe Cl ) }  ⋅ 0.5CVCl ⋅ 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).

Effect of reduction on the molecular structure and optical and magnetic properties of fluorinated copper(II) phthalocyanines.

The reduction of copper(ii) octafluoro- {CuII(F8Pc)} and hexadecafluorophthalocyanines {CuII(F16Pc)} by NaCpCo(CO)2 in the presence of cryptand[2.2.2] yields new crystalline {cryptand(Na+)}[CuII(F8Pc)˙3-]-·2C6H4Cl2 (1) and {cryptand(Na+)}2[CuII(F16Pc)4-]2-·C6H14 (2) salts.

Solid-State Properties of Hexaazatriphenylenehexacarbonitrile HAT(CN) Radical Anions in Crystalline Salts Containing Cryptand(M ) and Crystal Violet Cations.

Crystalline {Cryptand[2.2.2](Na )}{HAT(CN) }⋅0.

Decacyclene Radical Anions Showing Strong Low-energy Intramolecular Absorption and Magnetic Coupling of Spins in a Hexagonal Network.

Two salts of the aromatic hydrocarbon decacyclene, {cryptand[2.2.2](Cs )} (decacyclene ) (1) and {Bu MeP }(decacyclene ) (2), were obtained.

Strong magnetic coupling of spins in Fe(ii) dimers with differently charged thioindigo ligands.

A first coordination {[2.2.2]cryptand(K+)}2{FeII(TI˙-)(TI2-)}2·2C6H4Cl2 (1) complex of iron(ii) containing radical anions and dianions of thioindigo (TI) was obtained.

Cleavage of the C-H Bond in BuMeP by Zinc Porphyrin Dianions: Formation of {Zn(CHPBu)(TPyPH)} Containing Zn-C(ylide) Bond and the (TPyPH) Macrocycle Showing Strong NIR Absorption.

Reduction of {Zn(TPyP)} to the {Zn(TPyP)} dianions (TPyP: tetra(4-pyridyl)porphyrin) in the presence of BuMeP allows one to observe the C-H bond cleavage in the methyl group of BuMeP to form (BuMeP){Zn(CHPBu)(TPyPH)}·0.337CHCH (). Salt is the first coordination complex of neutral CHPBu ylide and metalloporphyrin.

Double-Decker Paramagnetic {(K)(H Hhp) } Radical Dianions Comprising Two [30]Trithia-2,3,5,10,12,13,15,20,22,23,25,30-Dodecaazahexaphyrins and a Potassium Ion.

Reduction of free-base [30]trithia-2,3,5,10,12,13,15,20,22,23,25,30-dodecaazahexaphyrin (H Hhp) yields {cryptand[2.2.2](K)} {(K)(H Hhp) }⋅4C H Cl (1) containing double-decker {(K)(H Hhp) } radical dianions, whose structure was elucidated using X-ray diffraction.

Molecular Structure and Magnetic and Optical Properties of Endometallonitridofullerene Sc N@I -C in Neutral, Radical Anion, and Dimeric Anionic Forms.

A series of compounds with Sc N@I -C in the neutral, monomeric, and dimeric anion states have been prepared in the crystalline form and their molecular structures and optical and magnetic properties have been studied. The neutral Sc N@I -C ⋅3 C H Cl (1) and (Sc N@I -C ) (TPC) ⋅5 C H Cl (2, TPC=triptycene) compounds both crystallized in a high-symmetry trigonal structure. The reduction of Sc N@I -C to the radical anion resulted in dimerization to form diamagnetic singly bonded (Sc N@I -C ) dimers.

{CpFe(CO)Sn(Macrocycle)} Radicals with Intrinsic Charge Transfer from CpFe(CO) to Macrocycles (Cp: Cp or Cp*); Effective Magnetic Coupling between Radical Trianionic Macrocycles.

Neutral {CpFe(CO)[Sn(Pc)]} {Cp is cyclopentadienyl (, ) or Cp* is pentamethylcyclopentadienyl (); Pc: phthalocyanine}, {Cp*Fe(CO)[Sn(Nc)]} (, Nc: naphthalocyanine), and {CpFe(CO)[Sn(TPP)]} (, TPP: tetraphenylporphyrin) complexes in which CpFe(CO) fragments (Cp: Cp or Cp*) are coordinated to Sn(macrocycle) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFe(CO) (Cp: Cp or Cp*) to [Sn(macrocycle)] to form the diamagnetic Fe and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain = 1/2 spins delocalized over the macrocycles.

Coordination-induced metal-to-macrocycle charge transfer and effect of cations on reorientation of the CN ligand in the {SnLMac} dianions (L = CN, OCN, Im; Mac = phthalo- or naphthalocyanine).

A series of anionic coordination complexes of tin(ii) phthalocyanine (Pc) with cyanide, cyanate, and imidazolate (Im) anions (1, 3, and 4, respectively) and tin(ii) naphthalocyanine (Nc) with cyanide anions (2) has been obtained. Two anions coordinate to tin(ii) atoms in 1-4 to form the {SnL2Mac}2- dianions in salts with the general formula {crypt[2.2.

Effect of One- and Two-Electron Reduction of Terbium(III) Double-Decker Phthalocyanine on Single-Ion Magnet Behavior and NIR Absorption.

Reduction of terbium(III) double-decker phthalocyanine, TbPc (1), by sodium fluorenone ketyl in the presence of bis(triphenylphosphoranylidene)ammonium cations yields one-electron-reduced (PPN){Tb(Pc)}·2.5CHCl (2) containing the dianionic Pc macrocycles, whereas a stronger NaCpCo(CO) reductant in the presence of an excess of cryptand yields two-electron-reduced {Cryptand(Na)}{(Pc)Tb(Pc)} (3) containing the Pc radical trianionic macrocycle. Isolated pairs of the {Tb(Pc)} anions are formed in 2, whereas compound 3 has unique 3D packing of the macrocycles with weak π-orbitals overlapping in all three directions.

Electronic Communication between S=1/2 Spins in Negatively-charged Double-caged Fullerene C Derivative Bonded by Two Single Bonds and Pyrrolizidine Bridge.

Radical anion salt {cryptand[2.2.2] (K )} (bispheroid) ⋅3.

Fullerene and endometallofullerene Kagome lattices with symmetry-forced spin frustration.

Salts of fullerene C60˙- and endometallofullerene Sc3N@Ih-C80˙- radical anions with Bu3MeP+ cations ((Bu3MeP+)3(C60˙-)3·C6H4Cl2 (1) and (Bu3MeP+)3(Sc3N@Ih-C80˙-)3·C6H4Cl2 (2)) have been obtained. The C3 symmetry of the Bu3MeP+ cation provides 2D Kagome lattices with an equilateral triangle arrangement of fullerenes in accordance with trigonal crystal symmetry P31m. The C60˙- and Sc3N@Ih-C80˙- radical anions preserve their monomeric forms in 1 and 2 with the S = 1/2 spin state down to 1.

Dianionic Titanyl and Vanadyl (Cation ) [M O(Pc )] Phthalocyanine Salts Containing Pc Macrocycles.

In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu N ) [M O(Pc )] (M=Ti, V) and (Bu MeP ) [M O(Pc )] (M=Ti, V) with [M O(Pc )] dianions were synthesized and characterized. Reduction of M O(Pc ) carried out with an excess of sodium fluorenone ketyl in the presence of Bu N or Bu MeP is exclusive to the phthalocyanine centers, forming Pc species. During reduction, the metal +4 charge did not change, implying that Pc is an non-innocent ligand.