Ionic compound containing iron phthalocyanine (FeIPc)− anions and (C70−)2 dimers. Optical and magnetic properties of (FeIPc)− in the solid state

Abstract

Ionic compounds containing the anion of iron phthalocyanine (Fe(I)Pc)(-), {(Fe(I)Pc)(-)}·(cryptand[2,2,2]·[Na(+)])·(C(6)H(4)Cl(2)) (1), and the fullerene C(70)(-) and Fe(I)Pc(-) anions, (C(70)(-))(2)·{(Fe(I)Pc)(-)}(6)·(cryptand[2,2,2]·[Na(+)])(8)·(C(6)H(4)Cl(2))(8.65)·(C(6)H(14))(0.35) (2), were obtained as single crystals. Their crystal structures and optical and magnetic properties were analyzed. Spectra of 1 and 2 manifest intense bands in visible-NIR range at 820, 690, 555, 528, 449, 400 and 316 nm attributed to (Fe(I)Pc)(-). The four-coordinate (Fe(I)Pc)(-) anions show an EPR signal with perpendicular and parallel components at g(⊥) = 2.487 and g(‖) = 2.353 in 1 and g(⊥) = 2.328 and g(‖) = 2.230 in 2. According to magnetic measurements the (Fe(I)Pc)(-) anions have low spin (S = 1/2) state indicating d(7) configuration for the Fe(I) atoms with the odd electron on the d(z(2)) orbital. Fullerene anions form singly bonded (C(70)(-))(2) dimers in 2, the shape of which efficiently fitted with the large planar phthalocyanine anions to be surrounded completely by eight (Fe(I)Pc)(-) anions. The (C(70)(-))(2) dimers are diamagnetic and EPR silent up to 350 K. Both complexes contain channels formed by four (Fe(I)Pc)(-) planes in 1 or four (Fe(I)Pc)(-) planes and two (C(70)(-))(2) dimers in 2. The channels are occupied by double chains of alternating cryptand[2,2,2]·[Na(+)] cations and solvent C(6)H(4)Cl(2) molecules.

Salt of Ring‐Reduced Iron(II) Octaethyltetrapyrazinoporphyrazine Containing Trimetallic Dianions with Peripherally Coordinated ZnCl2 Units: {FeII(TPyzPzEt8)4–(ZnCl2)2}2–

“…Potentially reduced metal phthalocyanines can also manifest promising conducting and magnetic properties. Metal macrocycles can be reduced successfully by strong reductants such as Na/Hg, potassium graphite (KC 8 ) , , LiCp * , decamethylchromocene,, and sodium fluorenone ketyl . Zinc dust can also be used as suitable reductant especially to obtain reduced compounds of iron(II) phthalocyanine or hexadecachlorophthalocyanine , …”

Synthesis of Iron(II) Octachlorotetrapyrazinoporphyrazine, Molecular Structure and Optical Properties of the (X−)2FeTPyzPACl8 Dianions with Two Axial Anionic Ligands (X− = CN−, Cl−)

“…Ligand-free FePc has slightly shorter average Fe-N(Pc) bonds of 1.926(1) Å. [17] Only half of FeTPyzPACl 8 is crystallographically independent. Label of atoms, type of bonds and the displacement of atoms from the 24-atom PA plane are shown in Figure 4, bond length and average length of definite types of bonds in this macrocycle are listed in Table 2.…”

“…[12] Now the salts with negatively charged cobalt(I), iron(I) and metal free phthalocyanines and porphyrazines have been obtained. [13][14][15][16][17][18][19] However, anionic phthalocyanines with tetra-coordinated metal atoms are not deeply investigated so far because of weak acceptor properties of metal phthalocyanine and as a result high air sensitivity of their anions. Metal-free phthalocyanines are reduced with potential more negative than -0.6 V, whereas zinc(II), copper(II), nickel(II) and manganese(II) phthalocyanines are reduced with potential -0.8 ÷ -0.9 V. [20] To increase the acceptor ability of metal macroheterocycles electron-withdrawing substituents such as Cl, F or CN can be attached to the phthalocyanine macrocycle or the number of nitrogen atoms in the macrocycle should be increased.…”

Ionic Interactions between Charged Phthalocyanine and Fullerene Derivatives

“…Similar charged anionic complexes of metal phthalocyanines and fullerenes were prepared and their crystal structures were analyzed. [7,10,11] For example, the anion of Fe(II) phthalocyanine (Fe I Pc -) and the anion of a fullerene could be obtained by reduction of the neutral compounds (Fe II Pc and fullerene) in solution with sodium fluorenone in the presence of a cryptand, and then isolation of single crystals. [11] For porphyrins few oppositely charged porphyrin-fullerene hybrids were described.…”

“…[7,10,11] For example, the anion of Fe(II) phthalocyanine (Fe I Pc -) and the anion of a fullerene could be obtained by reduction of the neutral compounds (Fe II Pc and fullerene) in solution with sodium fluorenone in the presence of a cryptand, and then isolation of single crystals. [11] For porphyrins few oppositely charged porphyrin-fullerene hybrids were described. [12,13] A positively charged porphyrin derivative and a negatively charged fullerene derivative form 1:1 aggregates, and association constants were determined.…”