Slow magnetic relaxation in a complex of photochromic spiropyran in a merocyanine form and cobalt(II) hexafluoroacetylacetonate.

The interaction between photochromic 8-methoxy-1',3',3'-trimethyl-6-nitro-spiro[chromene-2,2'-indole] (MNSP) and cobalt(II) hexafluoroacetylacetonate yields a deep red-violet solution due to the coordination-induced transition of MNSP from a colorless closed state to a colored open merocyanine (MC) form. The resulting complex {CoII(hfac)2·MNSP} (1) is obtained as crystals, and its structure at 250 K shows the coordination of two oxygen atoms from MNSP with CoII, forming a distorted octahedral surrounding around CoII. The unit cell of 1 contracts below 170 K by 5.5%, which is accompanied by shortening O-Co bonds and altering O-Co-O angles in the structure solved at 150 K. The χMT value of 3.06 emu K mol-1 at 300 K indicates the formation of high-spin CoII (S = 3/2) with a large orbital contribution characteristic of the octahedral surrounding. The contraction of the unit cell of 1 below 170 K provides a reversible 2.2% change of χMT in the 170-160 K range during heating and cooling regimes without hysteresis. The electron paramagnetic resonance signal of 1 was simulated with g-values of gx = 2.342, gy = 2.364, and gz = 2.084, and an isotropic g-factor of 2.267. The temperature-dependent χMT and field-dependent magnetization of 1 allow us to determine a positive zero-field splitting parameter of +20.1 cm-1. A study of the dynamic properties of 1 shows slow magnetic relaxation for CoII in a static field of 1000 Oe. Magnetic hysteresis loops were observed for 1 at 0.5 and 2 K; these loops are closed in the zero field region but opened at fields higher than ±100 and 700 Oe, respectively. The collapse of the loop is observed at 5 K. Excitation of the solution of 1 with green light decreases partially the intensity of the bands of the complex, whereas subsequent exposure of this solution to UV light partially restores these intensities.

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

Heterobimetallic {[Co(CO)4]-[InIII(Pc2-)]} (1) and (Cp*2Cr+){[Mn(CO)5]-[InIII(Pc˙3-)]}·2C6H4Cl2 (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 Pc2- macrocycles. Thus, the coordinated Co(CO)4 carbonyl accepts an electron in the one-electron reduction forming a diamagnetic [Co(CO)4]- anion. Complex 2 contains a heterobimetallic {[Mn(CO)5]-[InIII(Pc˙3-)]}- anion and paramagnetic Cp*2Cr+ counter cations. Therefore, in the double reduction, electrons are transferred to Mn(CO)5 forming a diamagnetic [Mn(CO)5]- anion and to the Pc2- macrocycle forming a paramagnetic radical Pc˙3- trianion. Such assignments for 1 and 2 are in line with optical spectra, crystal structures and the data of magnetic measurements. The spectrum of 1 in the UV-visible range is similar to that of the starting InIIIClPc. The formation of 2 is accompanied by an essential blue-shift of the Q-band of Pc as well as by the appearance of an intense NIR band at 1005 nm characteristic of Pc˙3-. Compound 1 is EPR silent and diamagnetic, whereas the value of the effective magnetic moment of 2 is 4.24µB at 300 K, which corresponds to the contribution of S = 1/2 (Pc˙3-) and S = 3/2 (Cp*2Cr+) spins. Both weakly coupled paramagnetic centers (J = -0.41 cm-1) are observed in the EPR spectra.

Synthesis, X-ray Structures, and Optical and Magnetic Properties of Cu(II) Octafluoro-octakisperfluoro(isopropyl)phthalocyanine: The Effects of Electron Addition and Fluorine Accretion.

The stepwise reduction of copper(II) 1,4,8,11,15,18,22,25-octafluoro-2,3,9,10,16,17,23,24-octakisperfluoro(isopropyl) phthalocyanine (CuIIF64Pc) in o-dichlorobenzene (C6H4Cl2) by potassium graphite in the presence of cryptand(K+), abbreviated L+, results in the formation of (L+)[CuII(F64Pc•3-)]-·2C6H4Cl2 (1), (L+)2[CuII(F64Pc4-)]2-·C6H4Cl2 (2), and (L+)2[CuII(F64Pc4-)]2- (3) complexes. Single-crystal X-ray structures revealed their composition and a monotonic increase with increased phthalocyanine (Pc) negative charges of the magnitude of alternative shortening and elongation of the prior equivalent Nmeso-C bonds. The complexes are separated by bulky i-C3F7 substituents, large cryptand counterions, and solvent molecules. Weak, new bands are generated in the visible and near-infrared (NIR) domains upon reductions. The one-electron reduced complex, [CuII(F64Pc•3-)]-, is a diradical, exhibiting broad electron paramagnetic resonance (EPR) signals, with intermediate parameters between those typical to CuII and F64Pc•3-. The two-electron reduced complexes, [CuII(F64Pc4-)]2-, contain a diamagnetic F64Pc4- macrocycle and a single spin, S = 1/2, on CuII. The bulky perfluoroisopropyl groups are suppressing intermolecular π-π interactions between Pcs in the [CuII(F64Pcn-)](n-2)- (n = 3, 4) anions, 1-3, similar to the case of the nonreduced complex. However, π-π interactions between 1 and o-dichlorobenzene are observed. The d9 and Pc electrons in 1 are antiferromagnetically coupled, J = -0.56 cm-1, as revealed by superconducting quantum interference device (SQUID) magnetometry, but the coupling is at least 1 order of magnitude smaller compared with the coupling observed for CuII(F8Pc•3-) and CuII(F16Pc•3-), a testimony to the F accretion effect of rendering the Pc macrocycle progressively more electron-deficient. The data for CuII(F64Pc) provide structural, spectroscopic, and magnetochemical insights, which establish a trend of the effects of fluorine and charge variations of fluorinated Pcs within the macrocycle series CuII(FxPc), x = 8, 16, 64. Diamagnetic Pcs might be useful for photodynamic therapy (PDT) and related biomedical applications, while the solvent-processable biradicalic nature of the monoanion salts may constitute the basis for designing robust, air-stable electronic, and magnetically condensed materials.

Negatively Charged Iron-Bridged Fullerene Dimer {Fe(CO)2-µ2-η2,η2-C60}22.

The interaction of {Cryptand(K+)}(C60•-) with Fe3(CO)12 produced {Cryptand(K+)}2{Fe(CO)2-µ2-η2,η2-C60}22-·2.5C6H4Cl2 (1) as the first negatively charged iron-bridged fullerene C60 dimer. The bridged iron atoms are coordinated to two 6-6 bonds of one C60 hexagon with short and long C(C60)-Fe bonds with average lengths of 2.042(3) and 2.088(3) Å. Fullerenes are close to each other in the dimer with a center-to-center interfullerene distance of 10.02 Å. Optical spectra support the localization of negative electron density on the Fe2(CO)4 units, which causes a 50 cm-1 shift of the C≡O vibration bands to smaller wavenumbers, and the C60 cages. Dimers are diamagnetic and electron paramagnetic resonance silent and have a singlet ground state resulting from the formation of an Fe-Fe bond in the dimer with a length of 2.978(4) Å. According to density functional theory calculations, the excited triplet state is higher than the ground state by 6.5 kcal/mol. Compound 1 shows a broad near-infrared band with a maximum at 970 nm, which is attributable to the charge transfer from the orbitals localized mainly on iron atoms to the C60 ligand.

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 {H2T(4-Py)P˙-} species are used as the starting material. A new solid-state supramolecular array [{H2T(4-Py)P}·{TbIII(TMHD)3}2]·2.84C6H14 (1) in which porphyrin units are bridged with TbIII ions to form a self-assembled 2D polymer has been obtained. The complex contains neutral porphyrin macrocycles, which is supported by optical and magnetic data. High-spin paramagnetic TbIII ions are weakly antiferromagnetically coupled in accordance with rather long distances between them.

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

The reaction of MnIIPc, FeIIPc or FeIIPcCl16 with KCN in the presence of cryptand[2.2.2] yielded dicyano-complexes {cryptand(K+)}2{MII(CN)2(macrocycle2-)}2-·XC6H4Cl2 (M = Mn and Fe, X = 1 and 2) that were used for the preparation of trinuclear assemblies of the general formula {cryptand(K+)}2{MII(CN)2Pc·(ML)2}2-·nC6H4Cl2 (MII = MnII and FeII; n = 1, 4 and 5). These assemblies were formed via coordination of two manganese(II) acetylacetonate (ML = MnII(acac)2, S = 5/2), tris(cyclopentadienyl)gadolinium (ML = Cp3GdIII, S = 7/2) or tris(cyclopentadienyl)neodymium (ML = Cp3NdIII, S = 3/2) units to the nitrogen atoms of bidentate cyano ligands. The N(CN)-Mn{MnII(acac)2} bond is 2.129(3) Å long but the bonds are elongated to 2.43-2.49 Å for tris(cyclopentadienyl)lanthanides. {Cryptand(K+)}2{MnII(CN)2Pc·(MnII(acac)2)2}2-·5C6H4Cl2 (2) contains three Mn(II) ions in different spin states (S = 5/2 and 1/2). Strong antiferromagnetic coupling of spins observed between them with the exchange interaction (J) of -17.6 cm-1 enables the formation of a high S = 9/2 spin state for {MnII(CN)2Pc·(MnII(acac)2)2}2- dianions at 2 K. The estimated exchange interaction between MnII (S = 1/2) and GdIII (S = 7/2) spins in {MnII(CN)2Pc·(Cp3GdIII)2}2- is only -1.1 cm-1, and in contrast to 2, nearly independent GdIII and MnII centers are formed. As a result, no transition to the high-spin state is observed in {MnII(CN)2Pc·(Cp3GdIII)2}2-. The {MnII(CN)2Pc·(Cp3NdIII)2}2- and{FeII(CN)2Pc·(Cp3NdIII)2}2- dianions with Cp3NdIII show a decrease of χMT values in the whole studied temperature range (300-1.9 K). A similar behaviour was found previously for pristine Cp3NdIII and Cp3NdIII·L complexes (L = alkylisocyanide ligand).

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 {SnII(Pc2-)}0 or radical anion {SnII(Pc˙3-)}- states is reported. Direct interaction of Co4(CO)12 with {SnII(Pc2-)}0 yields a crystalline complex {Co4(CO)11·SnII(Pc2-)} (1). There is no charge transfer from the cluster to phthalocyanine in 1, which preserves the diamagnetic Pc2- macrocycle. The Ru3(CO)12 cluster forms complexes with one or two equivalents of {SnII(Pc˙3-)}- to yield crystalline {Cryptand[2.2.2](Na+)}{Ru3(CO)11·SnII(Pc˙3-)}- (2) or {Cryptand[2.2.2](M+)}2{Ru3(CO)10·[SnII(Pc˙3-)]2}2-·4C6H4Cl2 (3) (M+ is K or Cs). Paramagnetic {SnII(Pc˙3-)}- species in 2 are packed in π-stacking [{SnII(Pc˙3-)}-]2 dimers, providing strong antiferromagnetic coupling of spins with exchange interaction J/kB = -19 K. Reduction of Ru3(CO)12, Os3(CO)12 and Ir4(CO)12 clusters by decamethylchromocene (Cp*2Cr) and subsequent oxidation of the reduced species by {SnIVCl2(Pc2-)}0 yield a series of complexes with high-spin Cp*2Cr+ counter cations (S = 3/2): (Cp*2Cr+){Ru3(CO)11·SnII(Pc˙3-)}-·C6H4Cl2 (4), (Cp*2Cr+){Os3(CO)10Cl·SnII(Pc˙3-)}-·C6H4Cl2 (5) and (Cp*2Cr+){Ir4(CO)11·SnII(Pc˙3-)}2- (6). It is seen that reduced clusters are oxidized by SnIV, which is transferred to SnII, whereas the Pc2- macrocycle is reduced to Pc˙3-. In the case of Os3(CO)12, oxidation of the metal atom in the cluster is observed to be accompanied by the formation of Os3(CO)10Cl with one OsI center. Rather weak magnetic coupling is observed between paramagnetic Cp*2Cr+ and {SnII(Pc˙3-)}- species in 4, but this exchange interaction is enhanced in 5 owing to Os3(CO)10Cl clusters with paramagnetic OsI (S = 1/2) also being involved in antiferromagnetic coupling of spins. The formation of {SnII(Pc˙3-)}- with radical trianion Pc˙3- macrocycles in 2-5 is supported by the appearance of new absorption bands in the NIR spectra and essential Nmeso-C bond alternation in Pc (for 3-5). On the whole, this work shows that both diamagnetic {SnII(Pc2-)}0 and paramagnetic {SnII(Pc˙3-)}- ligands substitute carbonyl ligands in the transition metal carbonyl clusters, forming well-soluble paramagnetic solids absorbing light in the visible and NIR ranges.

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.

Radical anion and dianion salts of titanyl macrocycles with acceptor substituents or an extended π-system.

Crystalline anionic salts of titanyl macrocycles with acceptor substituents or an extended π-system have been obtained for the first time: (PPN+)2{O[double bond, length as m-dash]TiIV(PcCl84-)}2- (1), (PPN+){O[double bond, length as m-dash]TiIV(Nc˙3-)}˙-·2C6H4Cl2 (2) and (PPN+)2{O[double bond, length as m-dash]TiIV(AceTPrzPz4-)}2-·1.3C6H4Cl2·0.8C6H5CN (3) where PPN+ is the bis(triphenylphosphoranylidene)ammonium cation, PcCl8 - 2,3,9,10,16,17,23,24-octachlorophthalocyanine; Nc - 2,3-naphthalocyanine, AceTPrzPz - tetra(acenaphthenopyrazino)porphyrazine. Salts 1-3 were obtained in the reduction of the parent titanyl macrocycles by fluorenone ketyl in the presence of an excess of PPNCl in o-dichlorobenzene with following precipitation of crystals with n-hexane. Reduction of macrocycles in 1-3 is accompanied by the appearance of intense NIR bands in the solid spectra at 963-1159 nm. It has been found that the extended π-system with linear annulation in {O[double bond, length as m-dash]TiIV(Nc˙3-)}˙- provides the shift of the NIR band to smaller energies (1159 nm) in comparison with those in the spectra of {O[double bond, length as m-dash]TiIV(Pc˙3-)}˙- (995-998 nm). Reduction of macrocycles leads also to the alternation of C-Nimine bonds due to partial disruption of their aromaticity. The disruption is higher for the dianions in 1 and 3 in comparison with the radical anions in 2. One-dimensional π-π stacking chains and layers are formed in 1 and 3 with diamagnetic {O[double bond, length as m-dash]TiIV(PcCl84-)}2- and {O[double bond, length as m-dash]TiIV(AceTPrzPz4-)}2- dianions, respectively. Salt 2 contains nearly isolated [{O[double bond, length as m-dash]TiIV(Nc˙3-)}˙-]2 dimers with a strong π-π interaction between paramagnetic radical anion macrocycles. As a result, a transition from the triplet to singlet state with antiparallel ordering of spins within the dimers is observed in 2 below 200 K.

The Salts of Copper Octafluoro- and Hexadecafluorophthalocyanines Containing [CuII(F8Pc)4-]2- Dianions and [CuF16Pc]- Monoanions.

Crystalline anionic salts with copper octafluoro- and hexadecafluorophthalocyanines, (Bu4N+)2[CuII(F8Pc)4-]2-·2C6H4Cl2 (1) and (PPN+)3[CuF16Pc]33-·2C6H5CN (2), where PPN+ is bis(triphenylphosphoranylidene)ammonium and Pc is phthalocyanine, have been obtained. The absence of noticeable absorption in the NIR range and DFT calculations for 1 indicate that both negative charges are mainly localized on the Pc ligand, and that the [CuII(F8Pc)4-]2- dianions are formed without reduction of CuII. The magnetic moment of 1.60 µB corresponds to the contribution of one S = 1/2 spin per dianion. The spin is localized on the CuII atom, which shows an EPR signal characteristic of CuII. Dianions are isolated in 1, providing only weak magnetic coupling of spins with a Weiss temperature of -4 K. Salt 2 contains closely packed π-π stacks built of [CuF16Pc]- anions of types I and II, and the interplanar distances are 3.187 and 3.275 Å. According to the DFT calculations, the [CuF16Pc]- anions of types I and II can have different charge distributions, with localization of an extra electron on the copper atoms to form diamagnetic [CuI(F16Pc)2-]- monoanions or delocalization of an extra electron on the F16Pc ligand to form [CuII(F16Pc)•3-]•- having an S = 1/2 (CuII) + 1/2 (F16Pc•3-) spin state. In fact, at 300 K, the magnetic moment of 2 of 3.25 µB per formula unit is rather close to the contribution from two [CuII(F16Pc)•3-]•- (calculated µeff is 3.46 µB). The Weiss temperature of -21.5 K indicates antiferromagnetic coupling of spins, which can be modeled by stronger intermolecular coupling between (F16Pc)•3- with J1/kB = -23.5 K and weaker intramolecular coupling between CuII and (F16Pc)•3- with J2/kB = -8.1 K. This interaction is realized in the {[CuII(F16Pc)•3-]•-}2 dimers separated by diamagnetic [CuI(F16Pc)2-]- species. In spite of the stacking arrangement of phthalocyanine macrocycles in 2, the inhomogeneous charge distribution and nonuniform distances between the macrocycles should suppress electrical conductivity.

Coordination Complexes of Transition Metals (M = Mo, Fe, Rh, and Ru) with Tin(II) Phthalocyanine in Neutral, Monoanionic, and Dianionic States.

The ability of tin atoms to form stable Sn-M bonds with transition metals was used to prepare transition metal complexes with tin(II) phthalocyanine in neutral, monoanionic, and dianionic states. These complexes were obtained via the interactions of [Sn(IV)Cl2Pc(3-)](•-) or [Sn(II)Pc(3-)](•-) radical anions with {Cp*Mo(CO)2}2, {CpFe(CO)2}2, {CpMo(CO)3}2, Fe3(CO)12, {Cp*RhCl2}2, or Ph5CpRu(CO)2Cl. The neutral coordination complexes of Cp*MoBr(CO)2[Sn(II)Pc(2-)]·0.5C6H4Cl2 (1) and CpFe(CO)2[Sn(II)Pc(2-)]·2C6H4Cl2 (2) were obtained from [Sn(IV)Cl2Pc(3-)](•-). On the other hand, the coordination of transition metals to [Sn(II)Pc(3-)](•-) yielded anionic coordination complexes preserving the spin on [Sn(II)Pc(3-)](•-). However, in the case of {cryptand[2,2,2](Na(+))}{CpFe(II)(CO)2[Sn(II)Pc(4-)]}(-)·C6H4Cl2 (4), charge transfer from CpFe(I)(CO)2 to [Sn(II)Pc(3-)](•-) took place to form the diamagnetic [Sn(II)Pc(4-)](2-) dianion and {CpFe(II)(CO)2}(+). The complexes {cryptand[2,2,2](Na(+))}{Fe(CO)4[Sn(II)Pc(3-)](•-)} (5), {cryptand[2,2,2](Na(+))}{CpMo(CO)2[Sn(II)Pc(2-)Sn(II)Pc(3-)(•-)]} (6), and {cryptand[2,2,2](Na(+))}{Cp*RhCl2[Sn(II)Pc(3-)](•-)} (7) have magnetic moments of 1.75, 2.41, and 1.75 µ(B), respectively, owing to the presence of S = 1/2 spins on [Sn(II)Pc(3-)](•-) and CpMo(I)(CO)2 (for 6). In addition, the strong antiferromagnetic coupling of spins with Weiss temperatures of -35.5 -28.6 K was realized between the CpMo(I)(CO)2 and the [Sn(II)Pc(3-)](•-) units in 6 and the π-stacking {Fe(CO)4[Sn(II)Pc(3-)](•-)}2 dimers of 5, respectively. The [Sn(II)Pc(3-)](•-) radical anions substituted the chloride anions in Ph5CpRu(CO)2Cl to form the formally neutral compound {Ph5CpRu(II)(CO)2[Sn(II)Pc(3-)]} (8) in which the negative charge and spin are preserved on [Sn(II)Pc(3-)](•-). The strong antiferromagnetic coupling of spins with a magnetic exchange interaction J/k(B) = -183 K in 8 is explained by the close packing of [Sn(II)Pc(3-)](•-) in the π-stacked {Ph5CpRu(II)(CO)2[Sn(II)Pc(3-)](•-)}2 dimers.

Synthesis, structures, and properties of crystalline salts with radical anions of metal-containing and metal-free phthalocyanines.

Radical anion salts of metal-containing and metal-free phthalocyanines [MPc(3-)](·-), where M = Cu(II), Ni(II), H2, Sn(II), Pb(II), Ti(IV)O, and V(IV)O (1-10) with tetraalkylammonium cations have been obtained as single crystals by phthalocyanine reduction with sodium fluorenone ketyl. Their formation is accompanied by the Pc ligand reduction and affects the molecular structure of metal phthalocyanine radical anions as well as their optical and magnetic properties. Radical anions are characterized by the alternation of short and long C-Nimine bonds in the Pc ligand owing to the disruption of its aromaticity. Salts 1-10 show new bands at 833-1041 nm in the NIR range, whereas the Q- and Soret bands are blue-shifted by 0.13-0.25 eV (38-92 nm) and 0.04-0.07 eV (4-13 nm), respectively. Radical anions with Ni(II), Sn(II), Pb(II), and Ti(IV)O have S = 1/2 spin state, whereas [Cu(II)Pc(3-)](·-) and [V(IV)OPc(3-)](·-) containing paramagnetic Cu(II) and V(IV)O have two S = 1/2 spins per radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal-free phthalocyanine radical anions [H2Pc(3-)](·-) (linewidth of 0.08-0.24 mT), broad EPR signals are manifested (linewidth of 2-70 mT) with g-factors and linewidths that are strongly temperature-dependent. Salt 11 containing the [Na(I)Pc(2-)](-) anions as well as previously studied [Fe(I)Pc(2-)](-) and [Co(I)Pc(2-)](-) anions that are formed without reduction of the Pc ligand do not show changes in molecular structure or optical and magnetic properties characteristic of [MPc(3-)](·-) in 1-10.

Molecular and ionic complexes of pyrrolidinofullerene bearing chelating 3-pyridyl units.

Molecular and ionic complexes of cis-2',5'-di(pyridin-3-yl)pyrrolidino[3',4':1,9](C(60)-I(h))[5,6]fullerene DP3FP with chlorobenzene (C(6)H(5)Cl), manganese(II) tetraphenylporphyrin (Mn(II)TPP) and tetrakis(dimethylamino)ethylene (TDAE) have been obtained for the first time. X-ray single crystal structure determination for the crystalline DP3FP·C(6)H(5)Cl (1) solvate proved unambiguously its molecular structure with the cis-arrangement of chelating 3-pyridyl groups. It has been demonstrated that DP3FP easily forms self-assembled photoactive complexes with metallated porphyrins. For example, the formation of a 1 : 1 complex between DP3FP and zinc (II) tetraphenylporphyrin (Zn(II)TPP) in cyclohexane solution (2) was evidenced using absorption spectroscopy. A successful X-ray single crystal structure determination was performed for a self-assembled triad composed of a DP3FP molecule linked with two Mn(II)TPP molecules in {DP3FP·(Mn(II)TPP)(2)}·(C(6)H(4)Cl(2))(3) (3). A strong organic donor TDAE reduces DP3FP to the radical anion state thus forming an ionic complex (TDAE˙(+))·(DP3FP˙(-))·(C(6)H(4)Cl(2))(1.6) (4). Optical, electronic and magnetic properties of 4 were investigated in detail. The performed studies strongly suggest that pyrrolidinofullerene DP3FP can be used as a building block in the design of various organic materials with advanced optoelectronic and/or magnetic properties.