ChemInform Abstract: PHTHALOCYANINE UND VERWANDTE VERBINDUNGEN 8. MITT. SUBSTITUIERTE PHTHALONITRILE

Mikhalenko, S. A.; Gladyr, S. A.; Luk’yanets, E. A.

doi:10.1002/chin.197223246

Cited by 9 publications

(9 citation statements)

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“…19 Twenty-five years later Hanack et al reported the preparation of 3,5-di-tert-butylphthalonitrile starting from 3,5-di-tert-butyl-2-bromoaniline, which was transformed into 3,5-di-tert-butyl-2-bromobenzonitrile by a diazotization reaction followed by standard the Sandmeyer reaction. 3,5-Di-tert-butyl-2-bromobenzonitrile can be easily converted into the target 3,5-di-tert-butyl-phthalonitrile using the Rosenmund-von Braun reaction and a similar synthetic strategy was used for preparation of the 3,5-dimethylphthalonitrile.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of substituted phthalocyanines

Nemykin¹,

Luk’yanets²

2010

Arkivoc

151

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This review summarizes the synthetic strategies for substituted phthalonitriles and phthalocyanines. Preparation of alkyl-, aryl-, halo-, nitro-, alkoxy-, aryloxy-, alkylthio-, arylthio-, and amino-substituted phthalocyanines along with the derivatives of phthalocyanine carboxylicand sulfoacids is overviewed. Influence of the substituents on the position of Q-band in UV-vis spectra of substituted phthalocyanines is also briefly discussed.

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Section: Methodsmentioning

confidence: 99%

Synthesis of substituted phthalocyanines

Nemykin¹,

Luk’yanets²

2010

Arkivoc

151

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“…Synthesis: Unsubstituted ZnPc (1) [50] and 3,6-diphenylphthalonitrile [51] were prepared according to the literature. The a-phenyl-substituted Pcs, with the exception of ZnPcPh 8 (6), were obtained by way of a mixed condensation reaction between phthalonitrile and 3,6-diphenylphthalonitrile.…”

Section: Methodsmentioning

confidence: 99%

Deformed Phthalocyanines: Synthesis and Characterization of Zinc Phthalocyanines Bearing Phenyl Substituents at the 1‐, 4‐, 8‐, 11‐, 15‐, 18‐, 22‐, and/or 25‐Positions

Fukuda

Homma

Kobayashi

2005

Chemistry A European J

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The synthesis of a series of zinc phthalocyanines partially phenyl-substituted at the 1-, 4-, 8-, 11-, 15-, 18-, 22-, and/or 25-positions (the so-called alpha-positions) is reported. Macrocycle formation based on 3,6-diphenylphthalonitrile, o-phthalonitrile, and zinc acetate predominantly yielded the near-planar disubstituted complex and opposite tetrasubstituted isomer, while the lithium method yielded the sterically hindered hexasubstituted complex and adjacent tetrasubstituted isomer. All compounds have been characterized by 1H NMR, MALDI-TOF-MS, and elemental analysis methods. In addition, crystal structures have been solved for the di-, hexa-, and octasubstituted complexes and the adjacent tetrasubstituted isomer. DFT geometry optimization calculations predict more highly deformed structures than those observed in the crystals. The packing force of the crystals cannot therefore be ignored, particularly for the less phenyl-substituted derivatives. The crystal structures have revealed that overlap of the phenyl groups causes substantial deformation of the phthalocyanine (Pc) ligands within the crystals, while strong pi-pi stacking in the remainder of the Pc moiety lacking phenyl substituents can suppress the impact of the deformation. Absorption spectra show sizable red shifts of the Q-band with increasing number of phenyl groups. Analysis of the results of absorption spectra and electrochemical measurements reveals that a substantial portion of the red shift is attributable to the ring deformations. Molecular orbital calculations lend further support to this conclusion. A moderately intense absorption band emerging at around 430 nm for highly deformed octaphenyl-substituted zinc Pc can be assigned to the HOMO-->LUMO+3 transition, which is parity-forbidden for planar Pcs, but becomes allowed since the ring deformations remove the center of symmetry.

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“…(ii) Materials. The so-called dicyanobenzo-15-crown-5 (2 equiv) 1e and diphenylmaleonitrile, 3,6-diphenylphthalonitrile, or 2,3-dicyano-1,4-diphenylnaphthalene (1 equiv) were fused in the presence of zinc- or copper acetate (0.5 equiv) at ca. 250−260 °C for 20−30 min.…”

Section: Methodsmentioning

confidence: 99%

Low Symmetrical Phthalocyanine Analogues Substituted with Three Crown Ether Voids and Their Cation-Induced Supermolecules

et al. 1996

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Unsymmetrical phthalocyanine analogues with three 15-crown-5 ether voids at the 3,4-positions (MtNIL, MtBZ, MtNAP) (Mt ) Zn, Cu) have been synthesized and characterized. Their dimerization is induced by addition of some cations, particularly Rb 2+ and K + . Cofacial dimer formation in the presence of these cations proceeds in a two-step three-stage process, as indicated by absorption and emission spectroscopy. These cofacial species have a highly specific C 2V eclipsed configuration providing well-defined dimeric species for spectroscopic analysis. The ESR spectra of the cation-induced dimeric copper derivatives show axial symmetry and may be analyzed in terms of interplanar separation of 4.2 Å. CuNAP alone forms a cofacial dimer even in the presence of Na + or Cs + , and the estimated interplanar distances are 4.1-4.2 Å without depending on the size of cations. The 1 H NMR spectra of zinc dimers are consistent with a cofacial configuration. Magnetic circular dichroism (MCD) spectra of C 2V type monomers can be interpreted as the superimposition of Faraday B-terms. Upper excited state (Soret, S 2 ) emission is observed for all zinc mononuclear species, and the quantum yield of S 1 emission is smaller than that of zinc phthalocyanine containing four crown units (ZnCRPc), suggesting that the lowering of molecular symmetry produces a decrease in quantum yield. Fluorescence decay of S 1 and S 2 emissions can be analyzed by mono-and biexponential fits, respectively. The zero field splitting (zfs) parameters, D, of the excited triplet (T 1 ) states of the monomers estimated from time-resolved EPR (TREPR) technique decrease in the order ZnNIL, ZnBZ, and ZnNAP, qualitatively indicating delocalization of excited π-electrons over additionally fused benzo and naphtho rings. A remarkable decrease in D value on dimerization is interpreted as an indication of delocalization of π-electrons over two macrocycles. Molecular orbital (MO) calculations within the framework of the Pariser-Parr-Pople (PPP) approximation succeed to reproduce the splitting, intensity, and the relative position of the Q absorption band of unsymmetrical monomers.

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ChemInform Abstract: PHTHALOCYANINE UND VERWANDTE VERBINDUNGEN 8. MITT. SUBSTITUIERTE PHTHALONITRILE

Cited by 9 publications

References 0 publications

Synthesis of substituted phthalocyanines

Synthesis of substituted phthalocyanines

Deformed Phthalocyanines: Synthesis and Characterization of Zinc Phthalocyanines Bearing Phenyl Substituents at the 1‐, 4‐, 8‐, 11‐, 15‐, 18‐, 22‐, and/or 25‐Positions

Low Symmetrical Phthalocyanine Analogues Substituted with Three Crown Ether Voids and Their Cation-Induced Supermolecules

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