Preparation and characterization of phthalocyanine-based organic alloy CoxNi1 − xPc(AsF6)0.5 (0 ≤ x ≤ 1)

Ding, Yuqin; Simonyan, Mkhital; Yonehara, Y.; Uruichi, Mikio; Yakushi, Kyuya

doi:10.1039/b100043h

Cited by 10 publications

(16 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Compound 1 ·DME has an inter-Pc ligand rotation angle of 44.7°, which is similar to that of other dimeric [(PcM) • ] 2 2+ species ,, and partially oxidized [PcM] n (•+) complexes and aggregates. − ,, As with other [PcM] •+ species, the complete overlap of the two Pc ligands prevents any dihedral ring distortion, and thus each ring maintains planarity. ,,, The five-coordinate Zn II centers sit 0.4 Å out of the Pc cavity; this disposition is perhaps induced by the axial DME coordination, which was observed for the [(PcCu II (ReO 4 )) • ] 2 and [(PcZnCl) • ] 2 complexes. , As with [(PcCu II (ReO 4 )) • ] 2 and [(PcZnCl) • ] 2 , the axial substitution of 1 ·DME prevented further aggregation. , …”

Section: Resultsmentioning

confidence: 65%

“…species 48,50,51 and partially oxidized [PcM] n(•+) complexes and aggregates. [54][55][56][57][58][59][60][61][62][63][64][65][66]71,74 As with other [PcM] •+ species, the complete overlap of the two Pc ligands prevents any dihedral ring distortion, and thus each ring maintains planarity. 50,51,72,73 The five-coordinate Zn II centers sit 0.4 Å out of the Pc cavity; this disposition is perhaps induced by the axial DME coordination, which was observed for the [ ( Figure 3).…”

Section: ■ Introductionmentioning

confidence: 99%

“…Focusing on the oxidized (and paramagnetic) ring in [PcM] •+ , partial oxidation of the PcM compounds to [PcM] n (•+) (where n < 1) has been investigated and a series of examples were structurally characterized. − The oxidation potential of PcM systems required to access these mixed-valent systems (containing both [PcM] •+ and PcM rings) is lower than the potential required to fully oxidize the material to [PcM] •+ compounds, making the mixed-valent species generally accessible by the use of oxidizing agents such as Br 2 and I 2 . The majority of structurally characterized [PcM] n (•+) compounds form stacks that are investigated for their conductivity properties, based on the opening of a conduction band between the ligands in the stack.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Ring-Oxidized Zinc(II) Phthalocyanine Cations: Structure, Spectroscopy, and Decomposition Behavior

et al. 2018

View full text Add to dashboard Cite

A bromonium oxidizing agent was used to produce a ring-oxidized zinc phthalocyanine (PcZn), [PcZn(solvent)][BAr] (1·solvent), in good yield. This material is dimeric in the solid state with one axially coordinated solvent [tetrahydrofuran (THF) or 1,2-dimethoxyethane (DME)] and close intradimer ring-ring distances of 3.18 and 3.136 Å (THF and DME respectively); this proximity facilitates strong antiferromagnetic coupling to yield diamagnetic dimers. 1·THF is present in solution as a monomer and a dimer. In CHCl, the dimer is favored above 0.1 mM, and it is almost exclusively present in solvents with a high dielectric constant such as acetonitrile. The material 1·THF/DME decomposes in DME to a meso-nitrogen-protonated species, [HPcZn(DME)][BAr] (2), which was isolated and represents the first example of such a structurally characterized, protonated, unsubstituted PcM complex. A partially oxidized dimer or "pimer" [(PcZn(DME))][BAr] (3) was also structurally characterized and has a intradimer ring-ring distance of 3.192 Å, similar to 1·THF/DME. Dimer 3 also represents the first isolated PcM-based pimer. Electron paramagnetic resonance analysis of a 1.0 mM solution of 1·DME in DME showed the production of 3 over hours by the combination of 1·DME and 2 in solution.

show abstract

Section: Resultsmentioning

confidence: 65%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Ring-Oxidized Zinc(II) Phthalocyanine Cations: Structure, Spectroscopy, and Decomposition Behavior

et al. 2018

View full text Add to dashboard Cite

show abstract

“…There are a handful of examples (Theocharis et al, 1984;Hasegawa et al, 1987) in which two compounds have different crystal structures and/or cell parameters but still form mixed crystals that contain two components. However, only in one example was the discrepancy between the unit-cell volumes of the two component crystals greater than 90 A Ê 3 (Ding et al, 2001). The CoÐCÐCÐCN conformation of 2ce3mpy is nearly cis, À81.91 (5) , while that of 2cp3mpy is almost trans, as shown in Fig.…”

Section: Molecular and Crystal Structures Of 2cp3mpy Mix-i And Mix-iimentioning

confidence: 90%

Modified photoreactivity due to mixed crystal formation. II. Enhanced reactivity upon conformational mimicry and cavity enlargement

Vithana

Uekusa

Sekine

et al. 2002

Acta Crystallogr Sect B

View full text Add to dashboard Cite

The 2-cyanopropyl (beta-cyanopropyl) group in the cobaloxime complex of (2-cyanopropyl)(3-methylpyridine)bis(dimethylglyoximato)cobalt(III) takes a trans conformation around the Co-C-C-CN bond in the crystal and undergoes isomerization to the 1-cyanopropyl (alpha-cyanopropyl) group with a low reaction rate when the powdered crystals are irradiated with a xenon lamp. When the complex was mixed with (2-cyanoethyl)(3-methylpyridine)bis(dimethylglyoximato)cobalt(III) or (2-cyanoethyl)(3-ethylpyridine)bis(dimethylglyoximato)cobalt(III), a mixed crystal, Mix-I or Mix-II, was obtained. The cell parameters of Mix-I and Mix-II were considerably different. When the crystals of Mix-I and Mix-II were irradiated with the xenon lamp, the 2-cyanopropyl group and the 2-cyanoethyl group isomerized to the 1-cyanopropyl and 1-cyanoethyl groups, respectively, in the crystalline state as well as in the solid state. The isomerization rates of the 2-cyanopropyl and 2-cyanoethyl groups of the mixed crystals became significantly higher than the corresponding rates in the component crystals. For the 2-cyanopropyl group, the conformational change from trans to cis in the mixed crystals caused reaction rates to be enhanced, and the expanded volume of the reaction cavity in the mixed crystals increased the reactivity for the 2-cyanoethyl group, when compared with the reactivity of each component crystal. A quantitative discussion of the increased rate constants is presented, which is based on the crystal structures. The shapes of the reaction cavities for the reactive groups undergoing isomerization control the conformation and configuration of the produced 1-cyanoethyl and 1-cyanopropyl groups.

show abstract

“…The crystal form of the alloys is orthorhombic for x < 0.25 and tetragonal for x > 0.45. 42 Thermoelectric power of [Co(Pc)] 2 (AsF 6 ) is ∼50 µV/K around room temperature, almost constant to 50 K, and then drops. 41,43 The dc conductivity 41,43 and microwave conductivity 43 exhibit activation-type temperature dependence (see Figure 18).…”

Section: [Co(pc)] 2 (Asf 6 )mentioning

confidence: 96%

PhthalocyaninesVersatile Components of Molecular Conductors

2004

View full text Add to dashboard Cite

Preparation and characterization of phthalocyanine-based organic alloy CoxNi1 − xPc(AsF6)0.5 (0 ≤ x ≤ 1)

Cited by 10 publications

References 24 publications

Ring-Oxidized Zinc(II) Phthalocyanine Cations: Structure, Spectroscopy, and Decomposition Behavior

Ring-Oxidized Zinc(II) Phthalocyanine Cations: Structure, Spectroscopy, and Decomposition Behavior

Modified photoreactivity due to mixed crystal formation. II. Enhanced reactivity upon conformational mimicry and cavity enlargement

PhthalocyaninesVersatile Components of Molecular Conductors

Contact Info

Product

Resources

About