A Phthalocyanine Producing Green, Ocher, and Red Colors Depending on the Central Metals

Fukuda, Takamitsu; Ono, Kunio; Homma, Shigetsugu; Kobayashi, Nagao

doi:10.1246/cl.2003.736

Cited by 36 publications

(25 citation statements)

References 9 publications

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“…[6] Reports on nonplanar substituted Pcs have begun to appear only recently. Cooks group reported the crystal structure of a conformationally stressed 1,4,8,11,15,18,22,25-octaisopentyl H 2 Pc, [7] while we independently reported a highly deformed a-octaphenylated H 2 Pc (H 2 PcPh 8 ). [8] Gorun and co-workers have since characterized the first dome-shaped metal-free Pc in the solid state.…”

Section: Introductionmentioning

confidence: 86%

“…[10] Metal PcPh 8 complexes also show unusual spectral band shifts, which are sufficiently large to result in red or ochre colors both in the solid phase and in solution. [11] These salient features of the a-phenyl-substituted Pc prompted us to investigate the relationship between the spectroscopic and electrochemical properties and the molecular structures. In this study, we report the synthesis of a series of a-phenyl-substituted ZnPcs 1-6 ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Introductionmentioning

confidence: 86%

Section: Introductionmentioning

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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“…A large red-shift has been attributed to highly deformed Pc skeleton due to the central metals not fitting into the cavity of the Pc molecule. The deformed Pc ligand then interacts with the protruding central metal, hence the observed red-shifting of the spectra [13].…”

Section: Change In Central Metalmentioning

confidence: 97%

Desired properties of new phthalocyanines for photodynamic therapy

Nyokong

2011

Pure and Applied Chemistry

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The manuscript focuses on the properties of phthalocyanines (Pcs) that are required for them to be employed as photosensitizers in applications such as photodynamic therapy (PDT). High triplet-state quantum yields and lifetimes as well as high singlet-oxygen quantum yields are required for a good photosensitizer. In addition, absorption of the photosensitizer in the red region of the electromagnetic spectrum is also required, and this can be achieved by ring expansion, substitution with electron-donating ligands, and change of the central metal among others. Quantum dots (QDs) are efficient accumulators of light energy, and they can transfer this energy to molecules that possess a very efficient ability to generate singlet oxygen through a process called Förster resonance energy transfer (FRET). Thus, there is a decrease in the fluorescence quantum yield of the QDs when in the vicinity of Pcs. Triplet quantum yields of the Pcs increase in the presence of QDs.

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“…Recently, red-coloured manganese Pcs for analogs, substituted with highly hindered, bulky hexadecaalkoxyl functional groups, have been reported (6, 1), while other red phthalocyanines bearing alkylthio (8) and phenyl groups (9) have been described, These analogs represent Pcs exhibiting pronounced red shifts. Previously, some highly red-shifted analogs of some Pcs had been prepared with some difficulty owing to insolubility (10) and decomposition problems (11 (12, l3).…”

Section: Introductionmentioning

confidence: 99%

“…Various metallated and nonmetallated Pcs bearing sterically bulky alkoxy moieties have been reported, including both neopentoxy and cyclohexylmethoxy groups (6,7). In addition to the effect that these substitutions appear to have on the absorption spectra of the resulting Pcs, a disruption of the n stacking among the aromatic macrocycles increases (5) in the presence of a base to generate 4,5-di-(1-adamantyloxy)-3,6-difluorophthalonitrile (6), 4,5-di-(1-adamantylamino)-3,6-difluorophthalonitrile (7), 4-(l -adamantylamino)-3,5,6-trifluorophthalonitrile (8), 3,4,5,6-retra-(l-adamantylmethoxy)phthalonitrile (9), or 3,4,5,6-tetra-f2-(l-adamantyl)ethoxy]phthalonitrile (10 Synthesis of 4,5-di-(1-adamantylamino)-3,6-difluorophthalonitrile (7) l-Adamantylamine (3, 1.52 g, 10.1 mmol, 2 equiv.) was dissolved in 15 Synthesis of 4-(1-adamantylamino)-3,5,6-trifluorophthalonitrile (8) l-Adamantylamine (3, 0.76 g, 5.0 mmol, 1 equiv.)…”

Section: Introductionmentioning

confidence: 99%

Syntheses and characterization of phthalonitriles and phthalocyanines substituted with adamantane moieties

Causey¹,

Dubovyk²,

Leznoff³

2006

Can. J. Chem.

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The reaction of 3,4,5,6-tetrafluorophthalonitrile with l-adamantanol, l-adamantylamine, l-adamantanemethanol, and l-adamantaneethanol gave 4,5-di-(1-adamantyloxy)-3,6-difluorophthalonitrile,4,5-di-(l-adamantylamino)-3,6-difluorophthalonitrile,4-(l-adamantylamino)-3,5,6-trifluorophthalonitrile, 3,4,5,6-tetra-(l-adamantylmethoxy)phthalonitrile, and 3,4,5,6+etra-(l-adamantylethoxy)phthalonitrile, respectively. The conversion of these tetrasubstituted phthalonitriles to magnesium, nickel, and metal-free phthalocyanines was demonstrated. These highly hindered phthalocyanines exhibited interesting red shifts in their UV-vis spectra.Key w ords : highly hindered adamantane phthalocyanines, adamantylphthalonitriles.R6sum6 : La r6action du 3,4,5,6+6trafluorophtalonitrile avec I'adamantan-1-ol, l'adamantyl-l-amine, I'adamantane-lmdthanol et l'adamantane-l-6thanol conduit i la formation des 4,5-di-(adamantanyl-l-oxy)-3,6-difluorophtalonitrile, 4,5-di-(adamantanyl-l-amino)-3,6-difluorophtalonitrile,4-(adamantanyl-l-amino)-3,5,6-trifluorophtalonitrile, 3,4,5,6-t6tra-(adamantanyl-l-mdthoxy)phtalonitrile, 3,4,5,6-t1tra-(adamantanyl-l-6thoxy)phtalonitrile respectivement. On a d6montr6qu'il est possible de transformer ces phtalonitriles t6trasusbstituds en phtalocyanines libre ou complex6es avec du nickel ou du magn6sium. Les spectres UV-visible de ces phtalocyanines fortement empdch6es pr6sentent des d6placements intdressants vers le rouge.Mofi cMs .' phtalocyanines de I'adamantane fortement emp0ch6es, adamantylphtalonitriles.lTraduit par la R6dactionl

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A Phthalocyanine Producing Green, Ocher, and Red Colors Depending on the Central Metals

Abstract: Metal complexes of a highly deformed 1,4,8,11,15,18,22,25-octaphenylphthalocyanine have been synthesized, and found to show various colors ranging from bright green, ocher, and red depending on the central metal employed.

Cited by 36 publications

References 9 publications

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

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

Desired properties of new phthalocyanines for photodynamic therapy

Syntheses and characterization of phthalonitriles and phthalocyanines substituted with adamantane moieties

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