Anomalously field-susceptible spin clusters emerging in the electric-dipole liquid candidate κ-(ET)2Hg(SCN)2Br.

Mutual interactions in many-body systems bring about various exotic phases, among which liquid-like states failing to order due to frustration are of keen interest. The organic system with an anisotropic triangular lattice of molecular dimers, κ-(ET)2Hg(SCN)2Br, has been suggested to host a dipole liquid arising from intradimer charge-imbalance instability, possibly offering an unprecedented stage for the spin degrees of freedom. Here, we show that an extraordinary unordered/unfrozen spin state having soft matter-like spatiotemporal characteristics emerges in this system. 1H nuclear magnetic resonance (NMR) spectra and magnetization measurements indicate that gigantic, staggered moments are nonlinearly and inhomogeneously induced by a magnetic field, whereas the moments vanish in the zero-field limit. The analysis of the NMR relaxation rate signifies that the moments fluctuate at a characteristic frequency slowing down to below megahertz at low temperatures. The inhomogeneity, local correlation, and slow dynamics indicative of middle-scale dynamical correlation length of several nanometers suggest novel frustration-driven spin clusterization.

Reaction of GaIIIClPc, SnIVCl2TPP and BIIIClSubPc with cyanide anions: reduction of macrocycles vs. formation of cyano-containing macrocyclic anions.

The reaction of GaIIIClPc, SnIVCl2TPP and BIIIClSubPc containing phthalocyanine (Pc), tetraphenylporphyrin (TPP) and subphthalocyanine (SubPc) macrocycles with cyanide in the presence of cryptand[2.2.2] under anaerobic conditions yields crystalline salts in which cyano anions substitute chloride anions at GaIII, SnIV or BIII, as well as reducing the macrocycles or adding one or two CN- to them. The reaction of GaIIICl(Pc2-) with CN- yields {crypt(K+)}{GaIIICN(Pc˙3-)}˙-·0.5C6H4Cl2 (1) in which the Pc2- macrocycle is reduced to Pc˙3-. Such reduction could probably occur through the addition of CN- to Pc2- forming {GaIII(CN)[Pc(CN)]3-}- which can decompose further interacting with an excess of CN-. As a result, Pc˙3- and cyanogene anions are formed. The interaction of SnIVCl2(TPP2-) with CN- is accompanied by the addition of CN- to the meso-carbon atom of porphyrin forming diamagnetic TPP(CN)3- macrocycles in {crypt(K+)}{SnIV(CN)2[TPP(CN)]3-}- (2). Salt 2 shows a strong NIR absorption band with the maximum at 854 nm whose intensity is comparable with that of the Soret band. The interaction of BIIICl(SubPc2-) with three equivalents of CN- is accompanied by the addition of two CN- to carbon atoms of SubPc2- closest to meso-nitrogen atoms forming {BIII(CN)[SubPc(CN)2]4-}2-. Most probably these dianions transfer electrons to C6H4Cl2 producing the {BIII(CN)[SubPc(CN)2]˙3-}˙- radical anions which form σ-bonded diamagnetic dianions in {crypt(K+)}2{BIII(CN)[SubPc(CN)2]}22-·3C6H4Cl2 (3). The remaining carbon atom closest to the meso-nitrogen atom is involved in this dimerization. According to the calculations, the energy of the C-CN bond is minimal for {GaIII(CN)[Pc(CN)]3-}- enabling further transformation of these anions to {GaIIICN(Pc˙3-)}˙- in 1, whereas cyano-containing anions in 2 and 3 with higher energy of this bond are stable towards the elimination of CN. Optical and magnetic properties of 1-3 together with their crystal and molecular structures are presented. The possible ways of the formation of 1-3 are discussed based on DFT calculations.

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. Together with two previously characterized salts of CuII(FxPc) (x = 8 and 16), this allows the study of the molecular structure and optical and magnetic properties of fluorinated copper phthalocyanines in different reduction states (-1 and -2). The blue shift of the Q-band increases together with the negative charge on the macrocycle, and new weak bands of the anions appear at 820-1013 nm. Alternation of the Nmeso-C bonds manifests itself in reduced macrocycles due to a partial disruption of macrocycle aromaticity. In the case of CuII(F8Pc) this effect is nearly two times stronger for dianions than for monoanions. The alternation of the bonds is less pronounced for perfluorinated CuII(F16Pc)n- (n = 1, 2) anions most probably due to a partial delocalization of the negative charge on fluoro-substituents. The reduction also noticeably elongates the average C-F bonds in CuII(F8Pc). The first reduction centered on the macrocycle leads to the formation of [CuII(F8Pc)˙3-]- in 1 with two S = 1/2 spins positioned on CuII and the radical trianion (F8Pc)˙3- macrocycle. As a result, a broad EPR signal is observed with g = 2.1652 at RT attributable to both paramagnetic species having exchange interactions. The formation of dimerized stacks from [CuII(F8Pc)˙3-]- in 1 results in strong enough magnetic coupling of the (F8Pc)˙3- spins within the dimers (J/kB = -21.8 cm-1), and weaker intramolecular coupling is observed between CuII and (F8Pc)˙3- (J/kB = -10.8 cm-1). Coupling between (F8Pc)˙3- spins from the neighboring dimers is nearly 1.5 times weaker (-14.6 cm-1). Under reduction conditions, a second electron also comes to the macrocycle forming diamagnetic F16Pc4- tetraanions. In this case S = 1/2 spin is preserved on CuII. Magnetic coupling between these centers is weak due to the long distances between them in the [CuII(F8Pc)4-]2- chains of 2. Salt 2 shows an EPR signal with a HF splitting characteristic of CuII with g∥ = 2.1806 (A∥ = 20.11 mT), and g⊥ = 1.9597 at RT.

Solid-State Properties of Hexaazatriphenylenehexacarbonitrile HAT(CN)6 .- Radical Anions in Crystalline Salts Containing Cryptand(M+ ) and Crystal Violet Cations.

Crystalline {Cryptand[2.2.2](Na+ )}{HAT(CN)6 .- }⋅0.5C6 H4 Cl2 (1), {Cryptand[2.2.2](K+ )}{HAT(CN)6 .- } (2), (CV+ ){HAT(CN)6 .- } (3), and (CV+ ){HAT(CN)6 .- }⋅2C6 H4 Cl2 (4) salts (where CV+ is the crystal violet cation) containing hexaazatriphenylenehexacarbonitrile radical anions have been obtained. The solid-state molecular structure as well as the optical and magnetic properties of HAT(CN)6 .- are studied. The formation of HAT(CN)6 .- in 1-4 leads to the appearance of new bands in the visible range, at 694 and 740 nm. The HAT(CN)6 .- radical anions have spin state S=1/2 and are packed in one-dimensional stacks containing the {HAT(CN)6 .- }2 dimers alternated with weaker interacting pairs of HAT(CN)6 .- in 1 and nearly isolated {HAT(CN)6 .- }2 dimers in 2. The {HAT(CN)6 .- }2 dimers are diamagnetic in 1 but they effectively mediate one-dimensional antiferromagnetic coupling of spins within the stacks with moderate exchange interaction of J/kB = -80 K. The behaviour of salt 2 is described by a singlet-triplet model for the {HAT(CN)6 .- }2 dimers with an energy gap of 434(±7) K. Magnetic behaviour of both salts agree well with the data of extended Hückel calculations. Salts 3 and 4 contain isolated stacks of alternated HAT(CN)6 .- and CV+ ions, and in this case, nearly paramagnetic behaviour is observed with Weiss temperatures of -1 and -7 K, respectively. Narrow Lorentzian EPR signals with g = 2.0033-2.0039 were found for the HAT(CN)6 .- radical anions in 1 and 4 but in solution g-factor shifts to 1.9964. The electronic structure of HAT(CN)6 .- is analysed based on X-ray diffraction data for 2, showing a Jahn-Teller distortion of the radical anion that reduces the symmetry from D3h to Cs and splits the initially degenerated LUMOs.

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 {Bu3 MeP+ }(decacyclene.- ) (2), were obtained. In both salts, decacyclene.- radical anions formed channels occupied by cations. However, corrugated hexagonal decacyclene.- layers could be outlined in the crystal structure of 1 with several side-by-side C⋅⋅⋅C approaches. The decacyclene.- radical anions showed strong distortion in both salts, deviating from the C3 symmetry owing to the repulsion of closely arranged hydrogen atoms and the Jahn-Teller effect. Radical anions showed intense unusually low energy absorption in the IR-range, with maxima at 4800 and 6000 cm-1 . According to the carculations, these bands can originate from the SOMO-LUMO+1 and SOMO-LUMO+2 transitions, respectively. Radical anions exhibited a S=1/2 spin state, with an effective magnetic moment of 1.72 µB at 300 K. The decacyclene.- spin antiferromagnetically coupled with a Weiss temperature of -11 K. Spin ordering was not observed down to 1.9 K owing to spin frustration in the hexagonal decacyclene.- layers.

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. The complex has two high-spin FeII centers bound by two oxygen atoms, and the TI˙- radical anions are coordinated to each FeII. As a result, the 4-spin system consisting of TI˙- (S = 1/2)-FeII (S = 2)-FeII (S = 2)-TI˙- (S = 1/2) coupled spins is formed within a dimer with strong FeII-FeII (J = -51.1 cm-1) and weaker FeII-TI˙- interactions of (J = -35.4 cm-1).

Cleavage of the C-H Bond in Bu3MeP+ by Zinc Porphyrin Dianions: Formation of {ZnII(CH2PBu3)(TPyPH)}- Containing Zn-C(ylide) Bond and the (TPyPH)3- Macrocycle Showing Strong NIR Absorption.

Reduction of {ZnII(TPyP)} to the {ZnII(TPyP)}2- dianions (TPyP: tetra(4-pyridyl)porphyrin) in the presence of Bu3MeP+ allows one to observe the C-H bond cleavage in the methyl group of Bu3MeP+ to form (Bu3MeP+){ZnII(CH2PBu3)(TPyPH)}-·0.337C6H5CH3 (1). Salt 1 is the first coordination complex of neutral CH2PBu3 ylide and metalloporphyrin. The released hydrogen atom attacks the meso-carbon atom of TPyP4- forming a TPyPH3- macrocycle related to phlorins. Decreased symmetry of the TPyPH3- allows the observation of a strong NIR absorption. We discuss the molecular structure, optical, and magnetic properties of 1 together with its formation pathways.

Double-Decker Paramagnetic {(K)(H3 Hhp)2 }⋠2- 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 (H3 Hhp) yields {cryptand[2.2.2](K)}2 {(K)(H3 Hhp)2 }⋅4C6 H4 Cl2 (1) containing double-decker {(K)(H3 Hhp)2 }⋅2- radical dianions, whose structure was elucidated using X-ray diffraction. Potassium ion forms 12 short (K+ )⋅⋅⋅N(H3 Hhp) contacts with two H3 Hhp macrocycles in the 3.048-3.157 Šrange. Dianions have S=1/2 spin state manifesting an effective magnetic moment of 1.64 µB at 300 K and a narrow Lorentzian electron paramagnetic resonance signal. Quantum chemical calculations support the ionic nature of the (K+ )-N(H3 Hhp) interactions and the nearly equal distribution of the -1.5 charge over each macrocycle. H3 Hhp takes the role of an aza-crown ether in free-base reduced state and forms a new type of double-decker complex.

Molecular Structure and Magnetic and Optical Properties of Endometallonitridofullerene Sc3 N@Ih -C80 in Neutral, Radical Anion, and Dimeric Anionic Forms.

A series of compounds with Sc3 N@Ih -C80 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 Sc3 N@Ih -C80 ⋅3 C6 H4 Cl2 (1) and (Sc3 N@Ih -C80 )3 (TPC)2 ⋅5 C6 H4 Cl2 (2, TPC=triptycene) compounds both crystallized in a high-symmetry trigonal structure. The reduction of Sc3 N@Ih -C80 to the radical anion resulted in dimerization to form diamagnetic singly bonded (Sc3 N@Ih -C80 - )2 dimers. In contrast to {[2.2.2]cryptand(Na+ )}2 (Sc3 N@Ih -C80 - )2 ⋅2.5 C6 H4 Cl2 (3) with strongly disordered components, we synthesized new dimeric phases {[2.2.2]cryptand- (K+ )}2 (Sc3 N@Ih -C80 - )2 ⋅2 C6 H4 Cl2 (4) and {[2.2.2]cryptand- (Cs+ )}2 (Sc3 N@Ih -C80 - )2 ⋅2 C6 H4 Cl2 (5) in which only one major dimer orientation was found. The thermal stability of the (Sc3 N@Ih -C80 - )2 dimers was studied by EPR analysis of 3 to show their dissociation in the 400-460 K range producing monomeric Sc3 N@Ih -C80 .- radical anions. This species shows an EPR signal with a hyperfine splitting of 5.8 mT. The energy of the intercage C-C bond was estimated to be 234±7 kJ mol-1 , the highest value among negatively charged fullerene dimers. The EPR spectra of crystalline (Bu3 MeP+ )3 (Sc3 N@Ih -C80 .- )3 ⋅C6 H4 Cl2 (6) are presented for the first time. The salt shows an asymmetric EPR signal, which could be fitted by three lines. Two lines were attributed to Sc3 N@Ih -C80 .- . Hyperfine splitting is manifested above 180 K due to the hyperfine interaction of the electron spin with the three scandium atoms (a total of 22 lines with an average splitting of 5.32 mT are observed at 220 K). Furthermore, each of the 22 lines is additionally split into six lines with an average separation of 0.82 mT. The large splitting indicates intrinsic charge and spin density transfer from the fullerene cage to the Sc3 N cluster. Both the monomeric and dimeric Sc3 N@Ih -C80 - anions show an intrinsic shift of the IR bands attributed to the Sc3 N cluster and new bands corresponding to these species appear in the NIR range of their UV/Vis/NIR spectra, which allows these anions to be distinguished from neutral species.

Coordination-induced metal-to-macrocycle charge transfer and effect of cations on reorientation of the CN ligand in the {SnL2Mac}2- 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[2.2.2](M+)}2{SnL2Mac}2- (M = K or Na; Mac: Pc or Nc; L = CN-, OCN-, Im-). The coordination of two ligands to SnII stabilizes these atoms in the higher tin(iv) oxidation state, providing transfer of two electrons from SnII to the macrocycle. The formation of tetraanionic (4-) macrocycles is accompanied by the appearance of new absorption bands in the NIR range, essentially blue-shifting both Soret and Q bands, and noticeable distortion in the macrocycles in 2-4, showing alternation of the C-C and C-N bonds. However, such distortions are not observed in 1. The absence of alternation in the case of 1 can be explained by the effect of uncompensated electric field from the surrounding cations, which stabilizes the macrocycle configuration with aligned bonds but nonuniform negative charge distribution on the imine nitrogen atoms. The cyanide ligand coordinates to SnPc by a nitrogen atom in 1, forming a Sn-N bond of 2.339(1) Å in length, whereas the cyanide ligand coordinates to SnNc by a carbon atom in 2, forming a shorter Sn-C bond of 2.266(3) Å in length. DFT calculations support the reorientation of the CN ligand in 1, which is induced by the electrostatic field of closely located cations.

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, TbIIIPc2 (1), by sodium fluorenone ketyl in the presence of bis(triphenylphosphoranylidene)ammonium cations yields one-electron-reduced (PPN+){TbIII(Pc2-)2}-·2.5C6H4Cl2 (2) containing the dianionic Pc2- macrocycles, whereas a stronger NaCpCo(CO)2 reductant in the presence of an excess of cryptand yields two-electron-reduced {Cryptand(Na+)}2{(Pc2-)TbIII(Pc•3-)}2- (3) containing the Pc•3- radical trianionic macrocycle. Isolated pairs of the {TbIII(Pc2-)2}- anions are formed in 2, whereas compound 3 has unique 3D packing of the macrocycles with weak π-orbitals overlapping in all three directions. This is the first example of the two-electron-reduced lanthanide double-decker containing Pc•3- radical trianion studied in solid state. Compound 2 manifests single-ion magnet (SIM) behavior with a large effective spin-reversal energy barrier of Ueff = 538 cm-1 in comparison with previously studied (Bu4N+){TbIII(Pc2-)2}- ( Ueff = 230 cm-1). Thus, changes in cation size and shape affect the molecular packing of {TbIII(Pc2-)2}- and increase the spin-reversal energy barrier. At the same time, two-electron-reduced species 3 containing TbIII and Pc•3- show no signs of SIM such as hysteresis loop at 1.9 K, and no peaks are observed on the temperature dependencies of in-phase (χ') and out-of-phase (χ″) signals. In contrast to EPR silent 2, both compounds 1 and 3 manifest broad signals from paramagnetic TbIII ions. Narrower signals attributed to Pc•3- are of high intensity only in 3. In addition to the absorption bands of Pc in the UV and visible spectral range, compound 3 manifests the lowest energy absorption band in solid-state spectra even in the near IR range at 4700 cm-1 (2130 nm), whereas such bands are not observed in the spectrum of 2. These data show that the reduction of the Pc macrocycles in the lanthanide double-deckers leads to the appearance of new very low-energy new transitions associated with Pc•3- whose energy is the lowest among known reduced metal phthalocyanines.

Electronic Communication between S=1/2 Spins in Negatively-charged Double-caged Fullerene C60 Derivative Bonded by Two Single Bonds and Pyrrolizidine Bridge.

Radical anion salt {cryptand[2.2.2] (K+ )}2 (bispheroid)2- ⋅3.5C6 H4 Cl2 (1) of the double-caged fullerene C60 derivative, in which fullerene cages are linked by a cyclobutane bridging cycle and additionally by a pyrrolizidine moiety, was obtained. Each fullerene cage in this derivative accepts one electron on reduction, thus forming the (bispheroid)2- dianions with two interacting S=1/2 spins on the neighboring cages. Low-temperature magnetic measurements reveal a singlet ground state of the bispheroid dianions whereas triplet contributions prevail at increased temperature. An estimated exchange interaction between two spins J/kB =-78 K in 1 indicates strong magnetic coupling between them, nearly two times higher than that (J/kB =-44.7 K) in previously studied (C60 - )2 dimers linked via a cyclobutane bridge only. The enhancement of magnetic coupling in 1 can be explained by a shorter distance between the fullerene cages and, possibly, an additional channel for the magnetic exchange provided by a pyrrolizidine bridge. Quantum-chemical calculations of the lowest electronic state of the dianions by means of multi-configuration quasi-degenerate perturbation theory support the experimental findings.

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 1.9 K. The close packing of the fullerene radical anions results in strong antiferromagnetic coupling of the spins with Weiss temperatures of -108 K for 1 and -43 K for 2. Compound 1 is a rare example of a magnetic system in which in spite of the strong magnetic coupling of spins no long-range ordering is observed down to 1.9 K. The 13C NMR spectra of the 13C enriched sample of 1 support the absence of the antiferromagnetic ordering of spins down to 1.5 K. Thus, the crystals of 1 preserve large spin frustration forced by the trigonal symmetry. Therefore, compound 1 is a promising candidate for the first observation of a quantum spin liquid (QSL) state in a fullerene-based system. Isostructural salt 2 is the first compound that contains monomeric paramagnetic Sc3N@Ih-C80˙- radical anions stable down to 1.9 K, which show strong spin frustration. These data indicate the ability of endometallofullerenes to give exotic magnetic systems such as QSLs.

Evidence for a quantum dipole liquid state in an organic quasi-two-dimensional material.

Mott insulators are commonly pictured with electrons localized on lattice sites, with their low-energy degrees of freedom involving spins only. Here, we observe emergent charge degrees of freedom in a molecule-based Mott insulator κ-(BEDT-TTF)2Hg(SCN)2Br, resulting in a quantum dipole liquid state. Electrons localized on molecular dimer lattice sites form electric dipoles that do not order at low temperatures and fluctuate with frequency detected experimentally in our Raman spectroscopy experiments. The heat capacity and Raman scattering response are consistent with a scenario in which the composite spin and electric dipole degrees of freedom remain fluctuating down to the lowest measured temperatures.

Dianionic Titanyl and Vanadyl (Cation+ )2 [MIV O(Pc4- )]2- Phthalocyanine Salts Containing Pc4- Macrocycles.

In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu4 N+ )2 [MIV O(Pc4- )]2- (M=Ti, V) and (Bu3 MeP+ )2 [MIV O(Pc4- )]2- (M=Ti, V) with [MIV O(Pc4- )]2- dianions were synthesized and characterized. Reduction of MIV O(Pc2- ) carried out with an excess of sodium fluorenone ketyl in the presence of Bu4 N+ or Bu3 MeP+ is exclusive to the phthalocyanine centers, forming Pc4- species. During reduction, the metal +4 charge did not change, implying that Pc is an non-innocent ligand. The Pc negative charge increase caused the C-N(pyr) bonds to elongate and the C-N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn-Teller effects are significant in the [eg(π*)]2 dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q-bands were observed in the UV/Vis/NIR when MIV O(Pc2- ) was reduced to [MIV O(Pc.3- )].- and [MIV O(Pc4- )]2- . From magnetic measurements, [TiIV O(Pc4- )]2- was found to be diamagnetic and (Bu4 N+ )2 [VIV O(Pc4- )]2- and (Bu3 MeP+ )2 [VIV O(Pc4- )]2- were found to have magnetic moments of 1.72-1.78 µB corresponding to an S=1/2 spin state owing to VIV electron spin. As a result, two latter salts show EPR signals with VIV hyperfine coupling.

Coordination Complexes of Titanium(IV) and Indium(III) Phthalocyanines with Carbonyl-Containing Dyes: The Formation of Singly Bonded Anionic Squarylium Dimers.

Reduction methods for the preparation of coordination complexes of titanium(IV) and indium(III) phthalocyanines (Pc) with organic dyes such as indigo, thioindigo, and squarylium dye III (SQ) have been developed, which allow one to obtain crystalline {cryptand(K+ )}{(cis-indigo-O,O)2- TiIV (Pc2- )}(Cl- )⋅C6 H4 Cl2 (1), {cryptand(K+ )}{(cis-thioindigo-O,O)2- InIII (Pc2- )}- ⋅C6 H4 Cl2 (2), and {cryptand(K+ )}{[(SQ)2 -O,O]2- InIII (Pc2- )}- ⋅3.5 C6 H4 Cl2 (3) complexes. The formation of these complexes is accompanied by the reduction of the starting dyes to the anionic state. Transition of trans-indigo or trans-thioindigo to the cis conformation in 1 and 2 provides coordination of both carbonyl oxygen atoms of the dye to TiIV Pc or InIII Pc. SQ is reduced to the radical anion state and forms unusual diamagnetic singly bonded (SQ- )2 dimers in 3. These dimers have two closely positioned carbonyl oxygen atoms coordinated to InIII Pc. Dianionic Pc2- macrocycles have been found in 1-3. The complexes contain two chromophore molecules at one metal center. However, their optical spectra are defined mainly by absorption bands of the metal phthalocyanines.

Synthesis and properties of N-methylimidazole solvates of vanadium(ii), chromium(ii) and iron(ii) phthalocyanines. Strong NIR absorption in VII(MeIm)2(Pc2-).

N-Methylimidazole (MeIm) solvates of vanadium(ii), chromium(ii) and iron(ii) phthalocyanines: [VII(MeIm)2(Pc2-)]0·MeIm (1) and [MII(MeIm)2(Pc2-)]0·2C6H4Cl2 (M = V (2), Cr (3), and Fe (4)) have been obtained and studied in a crystalline form. It has been shown that central metal atoms have the +2 oxidation state in 1-4 and dianionic Pc2- macrocycles are formed. Optical spectra of 1-3 (VII, CrII) are different from that of 4 (FeII) due to the appearance of intense absorption bands in the NIR range at 1187 nm for 1 and 2 and 1178 nm for 3 and manifestation of multiple bands in the visible range. Absorption in the NIR range is explained by unusually small gaps between the molecular orbitals at around HOMO and LUMO for MeIm solvated CrIIPc and VIIPc. The essential diradicaloid character of the Pc macrocycles in [CrII(MeIm)2(Pc2-)]0, in which α- and ß-orbitals are distributed in different regions of the macrocycle, has also been shown. In this case, the diradicaloid character is comparable to that of aromatic hydrocarbon heptacene. Magnetic properties of 1-3 are defined by metal atoms with a S = 3/2 spin state for VII and S = 1 for CrII. Compounds 1-3 manifest broad isotropic EPR signals at 4.2 K with g = 2.0188 and a linewidth (ΔH) of 81.8 mT for 1 (VII), g = 1.8300 and a linewidth ΔH = 161.0 mT for 2 (VII), and g = 2.0534 and ΔH = 60.27 mT for 3 (CrII). These signals shifted to smaller g-factors with the temperature increase. Integral intensity of narrow EPR signals from Pc˙3- does not exceed 0.1% from those of broad signals in 1-3. Complex 4 is EPR silent due to the presence of diamagnetic FeII and Pc2-.

Reaction of tin(iv) phthalocyanine dichloride with decamethylmetallocenes (M = CrII and CoII). Strong magnetic coupling of spins in (Cp*2Co+){SnIVCl2(Pc˙3-)}˙-·2C6H4Cl2.

The reaction of tin(iv) phthalocyanine dichloride {SnIVCl2(Pc2-)} with decamethylmetallocenes (Cp*2M, M = Co, Cr) has been studied. Decamethylcobaltocene reduces SnIVCl2(Pc2-) to form the (Cp*2Co+){SnIVCl2(Pc˙3-)}˙-·2C6H4Cl2 (1) complex. The negative charge of {SnIVCl2(Pc˙3-)}˙- is delocalized over the Pc macrocycle providing the alternation of the C-N(imine) bonds, the appearance of new bands in the NIR range and a strong blue shift of both the Soret and Q-bands in the spectrum of 1. The magnetic moment of 1 is equal to 1.68µB at 300 K, indicating the contribution of one S = 1/2 spin of the Pc˙3- macrocycles. These macrocycles form closely packed double stacks in 1 with effective π-π interactions providing strong antiferromagnetic coupling of spins at a Weiss temperature of -80 K. Decamethylchromocene initially also reduces SnIVCl2(Pc2-) to form the [(Cp*2Cr+){SnVICl2(Pc˙3-)}˙- complex but further reaction between the ions is observed. This reaction is accompanied by the substitution of one Cp* ligand of Cp*2Cr by chloride anions originating from {SnIVCl2(Pc˙3-)}˙- to form the complex {(Cp*CrCl2)(SnIV(µ-Cl)(Pc2-))}·C6H4Cl2 (2) in which the (Cp*CrCl2) and {SnIV(Pc2-)} species are bonded through the µ-bridged Cl- anion. According to the DFT calculations, this reaction proceeds via an intermediate [(Cp*2CrCl)(SnClPc)] complex.

Solid State Structure, and Optical and Magnetic Properties, of Free Base Tetra(4-pyridyl)porphyrin {H2T(4-Py)P}•- Radical Anions.

A crystalline {cryptand[2.2.2.](K+)}{H2T(4-Py)P•-}·C6H4Cl2 (1) salt with tetra(4-pyridyl)porphyrin radical anions was obtained, enabling the effect of reduction on a metal-free porphyrin macrocycle to be studied. In contrast to pristine H2T(4-Py)P, the H2T(4-Py)P•- radical anions have altered C-C(meso) bonds due to partial loss of aromaticity from the porphyrin macrocycle. Short and long bonds have average lengths of 1.396(3) and 1.426(3) Å, which thus differ by 0.03 Å. Reduction affects the positions of the Soret and Q-bands of porphyrin observed in the spectrum of 1 at 439 and 512, 583, and 614 nm, and new bands of the radical anion appear at 684, 755, and 900 nm. The H2T(4-Py)P•- radical anions have a spin state of S = 1/2 and a magnetic moment of 1.64 µB at 300 K. Salt 1 shows a narrow asymmetric EPR signal fitted with two Lorentzian lines, with g⊥ = 2.0031 and a line width (ΔH) of 0.186 mT, and g∥ = 2.0019 (ΔH = 0.284 mT) at 295 K, and this signal splits into three components below 39 K. Salt 1 shows antiferromagnetic spin coupling with a Weiss temperature of -2 K.

{CpFeII(CO)2SnII(Macrocycle•3-)} Radicals with Intrinsic Charge Transfer from CpFe(CO)2 to Macrocycles (Cp: Cp or Cp*); Effective Magnetic Coupling between Radical Trianionic Macrocycles•3.

Neutral {CpFeII(CO)2[SnII(Pc•3-)]} {Cp is cyclopentadienyl (1, 2) or Cp* is pentamethylcyclopentadienyl (3); Pc: phthalocyanine}, {Cp*FeII(CO)2[SnII(Nc•3-)]} (4, Nc: naphthalocyanine), and {CpFeII(CO)2[SnII(TPP•3-)]} (5, TPP: tetraphenylporphyrin) complexes in which CpFeII(CO)2 fragments (Cp: Cp or Cp*) are coordinated to SnII(macrocycle•3-) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFeI(CO)2 (Cp: Cp or Cp*) to [SnII(macrocycle2-)] to form the diamagnetic FeII and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain S = 1/2 spins delocalized over the macrocycles. This provides alternation of the C-Nimine or C-Cmeso bonds in the macrocycles, the appearance of new bands in the near-infrared spectra of the complexes, and blue shift of both Soret and Q-bands. The {CpFeII(CO)2SnII(macrocycle•3-)} units (Cp: Cp or Cp*, macrocycle: Pc or Nc) form closely packed π-stacking dimers in 1 and 3 or one-dimensional chains in 2 and 4 with effective π-π interaction between the macrocycles. Such packing allows strong antiferromagnetic coupling between S = 1/2 spins. Magnetic interaction can be described well by the Heisenberg model for the isolated dimers in 1 and 3 with exchange interaction J/k B = -78 and -85 K, respectively. Magnetic behavior of 2 and 4 is described well by the model that includes contributions from an antiferromagnetically coupled S = 1/2 dimer (J intra) and a Heisenberg S = 1/2 chain with alternating antiferromagnetic spin exchange between the neighbors (J inter). Compound 2 demonstrates large intradimer interaction of J intra/k B = -54 K and essentially weaker interdimer exchange interactions of J inter/k B = -6 K, whereas compound 4 shows strong magnetic coupling of spins within the dimers (J intra/k B = -170 K) as well as between the dimers (J inter/k B = -40 K). Compound {CpFeII(CO)2[SnII(TPP•3-)]} (5) shows no π-π interactions between the porphyrin macrocycles, and magnetic coupling is weak in this case (Weiss temperature is -5 K). Preparation of a similar complex with indium(III) chloride phthalocyanine yields {CpFe(CO)2[In(Pc2-)]} (6). In this complex, indium(III) atoms are reduced instead of the phthalocyanine macrocycles that explains electron paramagnetic resonance silence of 6 in the 4-295 K range.