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

Konarev, Dmitri V.; Troyanov, Sergey I.; Kuzmin, Alexey V.; Nakano, Yoshiaki; Ishikawa, Masaru; Faraonov, Maxim A.; Khasanov, Salavat S.; Litvinov, Alexey L.; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N.

doi:10.1021/acs.inorgchem.6b01932

Cited by 16 publications

(29 citation statements)

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“…The line is split into four lines with an essentially larger HFS constant A ⊥ = 16.7 mT, and the position of the parallel component of the EPR signal can be determined as g ∥ = 2.2626 at 12 K (Figure ). Interestingly, the A ∥ value is slightly lower than the splitting constant for Cu II in reduced copper(II) phthalocyanines ( A ∥ = 20–26 mT). , The splitting for g ⊥ is approximately 5.4 times smaller in 2 than that for the component with g ∥ . The observation of splitting for the perpendicular component of the signal is rare for mononuclear Cu II complexes, and the difference in the HFS constants can reach up to 7.3 times ( A ∥ = 37.7 mT and A ⊥ ∼ 5.14 mT) .…”

Section: Resultssupporting

confidence: 69%

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Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

et al. 2021

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Metal complexes of trithiadodecaazahexaphyrin (Hhp) that contain M II 3 O clusters inside a π-extended trianionic (Hhp 3− ) macrocycle have been prepared. Studies of the magnetic properties of Ni II 3 O(Hhp) and Cu II 3 O(Hhp) reveal a diamagnetic and EPR-silent trianionic (Hhp 3− ) macrocycle and diamagnetic Ni II 3 (O 2− ) or paramagnetic Cu II 3 (O 2− ) tetracations. The positive charge of M II 3 O(Hhp) is compensated by one acetate anion {M II 3 O(Hhp)} + (CH 3 CO 2 − ). The three-electron reduction of {M II 3 O(Hhp)} + yields {cryptand 2) crystalline salts. The magnetic properties of 1 reveal the formation of Hhp 5− and the reduction of nickel(II) to the paramagnetic Ni I ion (S = 1/2), which is accompanied by the formation of the {Ni II 2 Ni I O(Hhp 5− )} 2− dianion. As a result, the magnetic moment of 1 is 1.68 μ B in the 20−220 K range, and a broad EPR signal of Ni I was observed. The Hhp 5− macrocycle has a singlet ground state, but the increase in the magnitude of the magnetic moment of 1 above 220 K is attributed to the population of the triplet excited state in Hhp 5− . The {Ni II 2 Ni I O(Hhp 5− )} 2− dianion is transferred from the doublet excited state to the quartet excited state with an energy gap of 1420 ± 50 K. Salt 1 also shows an unusually strong low-energy NIR absorption, which was observed at 1000−2200 nm. In 2, a highly reduced Hhp •6− radical hexaanion (S = 1/2) coexists with a Cu II 3 (O 2− ) cluster (S = 1/2) in the {Cu II 3 O(Hhp •6− )} 2− dianions. The dianions have a triplet ground state with antiferromagnetic exchange between two S = 1/2 spins with J = −6.4 cm −1 . The reduction of Hhp in both salts equalizes the initially alternated C−N bonds, supporting the increase in the Hhp macrocycle electron delocalization.

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Section: Resultssupporting

confidence: 69%

“…Other fitting parameters are the orbital reduction parameter σ = −0.27 and the spin–orbit coupling parameter λ 1 = −553 cm –1 at g = 2.13 for the Cu II atoms. The magnitude of this exchange is comparable with those found for the reduced copper(II) phthalocyanines. , …”

Section: Resultsmentioning

confidence: 99%

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

et al. 2021

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“…5 Recently, we prepared (Cp*Ir III I 2 )-[Sn II Pc(2−)]•2C 6 H 4 Cl 2 , the first crystalline neutral coordination complex in which two metal-containing fragments are bound via an Sn−Ir bond with a length of 2.58 Å. 7 Thus, transition metal complexes are obtained from neutral metal porphyrins and phthalocyanines. 5−7 However, such complexes with radical anions of metal phthalocyanine remain unknown, and synthetic routes for their preparation have not yet been developed.…”

Section: ■ Introductionmentioning

confidence: 99%

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

Konarev¹,

Kuzmin²,

Nakano

et al. 2016

Inorg. Chem.

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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.

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“…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 , …”

Section: Introductionmentioning

confidence: 99%

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

et al. 2019

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Reduction of iron(II) octaethyltetrapyrazinoporphyrazine, FeIITPyzPzEt8, by zinc dust allowed the preparation of crystalline salt (PPN+)2{FeII(TPyzPzEt8)4–(ZnCl2)2}2– (1) (PPN+ is bis(triphenylphosphoranylidene)ammonium). Metal atom zinc transfers two electrons to FeIITPyzPzEt8 forming the {Fe(TPyzPzEt8)}2– dianions which coordinate two ZnCl2 units on the periphery of the TPyzPzEt8 macrocycle. Tetrahedral environment around the zinc(II) atoms is formed with the length of the Zn–N bonds of 2.071(7) Å with meso‐ and 2.304(8) Å with pyrazine nitrogen atoms of TPyzPzEt8. Optical and EPR spectra show the formation of diamagnetic tetraanionic {TPyzPzEt8}4– macrocycle in 1, and as a result, two‐electron reduction of FeIITPyzPzEt8 is centered exclusively on the macrocycle. According to DFT calculations for the {Fe(TPyzPzMe8)(ZnCl2)2}2– and {Fe(TPyzPzMe8)}2– dianions the reason of that is strongly increased electron affinity of the TPyzPzMe8 macrocycle at the coordination of two ZnCl2 units. Obviously, this situation is different from iron(II) phthalocyanine which shows metal‐centered first and second reduction.

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The Salts of Copper Octafluoro- and Hexadecafluorophthalocyanines Containing [Cu^II(F₈Pc)^4–]^2– Dianions and [CuF₁₆Pc]⁻ Monoanions

Cited by 16 publications

References 45 publications

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

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

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

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

Cited by 16 publications

References 45 publications

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear MII3O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear MII3O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

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

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

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The Salts of Copper Octafluoro- and Hexadecafluorophthalocyanines Containing [Cu^II(F₈Pc)^4–]^2– Dianions and [CuF₁₆Pc]⁻ Monoanions

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

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