Synthesis, structure, and spectroscopic properties of (.sigma.-alkyl)iron(II) phthalocyanines

Tahiri, Mohamed; Doppelt, P.; Fischer, J. R.; Weiss, R.

doi:10.1021/ic00289a030

Cited by 37 publications

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“…Thus, the tendency of Fe–N bond lengths, the strict differences in the molecular shape, and the arrangement of the nearby located cations points to the coexistence of differently charged FeCl 16 Pc units. The differences in the Fe–N bond lengths do not allow to distinguish mono‐ and dianions of FeCl 16 Pc 6. However, the saddle‐like conformation of the Pc macrocycle is characteristic of the (Fe I Cl 16 Pc) – monoanions in previously studied salts13 and in 1 .…”

Section: Resultsmentioning

confidence: 96%

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Layered Salts with Iron Hexadecachlorophthalocyanine Anions – The Formation of [{FeCl₁₆Pc}₂]^3– Dimers Containing [Fe^ICl₁₆Pc(2–)]^– and Diamagnetic [Fe⁰Cl₁₆Pc(2–)]^2–

et al. 2014

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Iron hexadecachlorophthalocyanine (Cl16Pc) salts with a layered arrangement of phthalocyanine (Pc) macrocycles were obtained by the reduction of FeCl16Pc with sodium fluorenone ketyl in the presence of PPNCl [PPN+: bis(triphenylphosphine)iminium cation] and TBABr (TBA+: tetrabutylammonium cation). (PPN+)[(FeICl16Pc)–]·0.78C6H4Cl2·0.22C6H14 (1) contains π–π stacking columns formed by dimerized (FeICl16Pc)– anions. The side‐by‐side arrangement of neighboring columns results in the formation of a layered iron hexadecachlorophthalocyanine structure. (TBA+)3{[(FeCl16Pc)2]3–} (2) contains hexagonal layers formed by [(FeCl16Pc)2]3– dimers and separated by TBA+ cations. The dimers bear –3 charge and, according to optical and X‐ray diffraction data, consist of a [FeI(Cl16Pc)]– monoanion and a [Fe0(Cl16Pc)]2– dianion. These anions are bonded in the dimer by a Fe–Fe bond of 2.899(4) Å length. It was shown that the negative charge in both anions is localized on the iron atoms to form FeI and Fe0, respectively, and no electron transfer to the hexadecachlorophthalocyanine macrocycles is observed. Magnetic data indicate the presence of only one S = 1/2 spin per [(FeCl16Pc)2]3– dimer. This result is in agreement with the formation of iron(I) and iron(0) hexadecachlorophthalocyanine anions, which have the iron atoms in d7 and diamagnetic d8 electron configuration, respectively. The spins of the iron(I) atoms are arranged in a hexagonal manner and only weakly interact, which results in a Weiss temperature of –1 K because of the long distances between them (>18 Å). Previously studied anionic salts with a columnar arrangement of [FeI(Cl16Pc)]– do not show EPR signals from FeI. In contrast, salt 2 shows an intense EPR signal with main components at g⟂ = 2.249 and g∥ = 1.989, which are characteristic of FeI with d7 electron configuration.

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Section: Resultsmentioning

confidence: 96%

“…Anionic phthalocyanines with tetracoordinated metals have not been investigated so much because of their high air sensitivity 6–14. Theoretical works predict metallic conductivity and even superconductivity for electron‐doped metal phthalocyanines 15.…”

Section: Introductionmentioning

confidence: 99%

Layered Salts with Iron Hexadecachlorophthalocyanine Anions – The Formation of [{FeCl₁₆Pc}₂]^3– Dimers Containing [Fe^ICl₁₆Pc(2–)]^– and Diamagnetic [Fe⁰Cl₁₆Pc(2–)]^2–

et al. 2014

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“…40 Other reagents, including sodium fluorenone, 41 zinc dust 42 and potassium t-butylthiolate 13 have also been employed to chemically generate isolable reduced PcM complexes. Borohydride-based reagents have been used as reducing agents in the isolation of other PcM complexes, such as in the preparation of [ n Bu 4 N]PcCo from PcCo and [ n Bu 4 N]BH 4 .…”

Section: Introductionmentioning

confidence: 99%

Reducing zirconium(iv) phthalocyanines and the structure of a Pc⁴⁻Zr complex

et al. 2015

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The synthesis and characterization of the ring-unsubstituted zirconium phthalocyanine PcZrCl2 (; Pc(x-) = phthalocyaninato(x-)) and its reduction products are described. X-ray analysis of (crystallized from hot 1-chloronaphthalene) reveals that is a chloride-bridged dimer [PcZrCl]2(μ-Cl)2 in the solid-state; was also characterized by UV-vis/MCD spectroscopy and cyclic voltammetry, which indicated reduction potentials at -0.55, -0.95 and -1.28 V. Although attempts to access these Pc-ring reduced species with KC8 led to mixtures of reduced products due to the insolubility of both starting materials, one equivalent of the reducing agent KEt3BH reacted with to generate Pc(3-)-containing species, as indicated by visible Q-band spectral changes (from λmax = 686 for to 589/611 nm), a single ESR peak (g = 2.001) and paramagnetically shifted (1)H NMR resonances consistent with the presence of a Pc-radical anion. Addition of two equivalents of KEt3BH to generated Pc(4-)-containing species, confirmed by a shift in λmax to 522 nm and upfield-shifted (1)H NMR peaks relative to . Reaction of with one and two equivalents of LiCp* did not generate Cp*-substituted products but also effected reduction to analogous Pc(3-) and Pc(4-) species. This latter material, the air-sensitive ring di-reduced "ate"-complex Pc(4-)Zr(LiCl)1.5(DME)3, of the form [LiCl(DME)4]0.5[Pc(4-)ZrClLi(DME)] was structurally characterized, illustrating partial bond localization in the Pc(4-) ring, which also adopts a saddle-shape vs. the more typical dome-configuration found in . This represents a rare example of an isolated and structurally characterized Pc(4-) complex.

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“…[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.…”

Section: Introductionmentioning

confidence: 99%

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

Ustimenko¹,

Konarev

Khasanov³

et al. 2013

MHC

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Synthesis, structure, and spectroscopic properties of (.sigma.-alkyl)iron(II) phthalocyanines

Cited by 37 publications

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Layered Salts with Iron Hexadecachlorophthalocyanine Anions – The Formation of [{FeCl₁₆Pc}₂]^3– Dimers Containing [Fe^ICl₁₆Pc(2–)]^– and Diamagnetic [Fe⁰Cl₁₆Pc(2–)]^2–

Layered Salts with Iron Hexadecachlorophthalocyanine Anions – The Formation of [{FeCl₁₆Pc}₂]^3– Dimers Containing [Fe^ICl₁₆Pc(2–)]^– and Diamagnetic [Fe⁰Cl₁₆Pc(2–)]^2–

Reducing zirconium(iv) phthalocyanines and the structure of a Pc⁴⁻Zr complex

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

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Synthesis, structure, and spectroscopic properties of (.sigma.-alkyl)iron(II) phthalocyanines

Cited by 37 publications

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Layered Salts with Iron Hexadecachlorophthalocyanine Anions – The Formation of [{FeCl16Pc}2]3– Dimers Containing [FeICl16Pc(2–)]– and Diamagnetic [Fe0Cl16Pc(2–)]2–

Layered Salts with Iron Hexadecachlorophthalocyanine Anions – The Formation of [{FeCl16Pc}2]3– Dimers Containing [FeICl16Pc(2–)]– and Diamagnetic [Fe0Cl16Pc(2–)]2–

Reducing zirconium(iv) phthalocyanines and the structure of a Pc4−Zr complex

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

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Layered Salts with Iron Hexadecachlorophthalocyanine Anions – The Formation of [{FeCl₁₆Pc}₂]^3– Dimers Containing [Fe^ICl₁₆Pc(2–)]^– and Diamagnetic [Fe⁰Cl₁₆Pc(2–)]^2–

Layered Salts with Iron Hexadecachlorophthalocyanine Anions – The Formation of [{FeCl₁₆Pc}₂]^3– Dimers Containing [Fe^ICl₁₆Pc(2–)]^– and Diamagnetic [Fe⁰Cl₁₆Pc(2–)]^2–

Reducing zirconium(iv) phthalocyanines and the structure of a Pc⁴⁻Zr complex