Syntheses of Octa(dialkylamino)azaphthalocyanines

The synthesis of octaazaphthalocyanine (AzaPc) derivatives, with bulky phenoxyl substituents placed at eight peripheral positions and containing either H(+), Ni(2+) or Zn(2+) ions in their central cavity, is described. The required precursors, derivatives of pyrazine-2,3-dicarbonitrile, were prepared using a nucleophilic aromatic substitution reaction between 2,6-diisopropylphenol or 2,6-diphenylphenol and 5,6-dichloropyrazine-2,3-dicarbonitrile. Analysis of the resulting AzaPcs by UV/Visible and (1)H NMR spectroscopy confirms that steric isolation of the AzaPc cores was enforced both in solution and in the solid state. X-ray diffraction studies of single crystals of the AzaPcs reveal that solvent inclusion takes place in each case. Of particular significance is the finding that the zinc derivative of 2,3,9,10,16,17,23,24-octa-(2,6-diisopropylphenoxy)octaazaphthalocyanine provides nanoporous cubic crystals, containing massive (8 nm(3)) solvent-filled voids, similar to those of the analogous phthalocyanine derivative. Exchange of the included solvent within the voids can be readily achieved by using a number of alternative solvents including water. Based on the observed loading of included water, the internal volume of this nanoporous cubic crystal appears to be more hydrophilic than its phthalocyanine counterpart.

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Synthesis and J‐Dimer Formation of Tetrapyrazinoporphyrazines with Different Functional Groups for Potential Biomolecular Probe Applications

Demuth

Miletín

Machan

et al. 2020

ChemPlusChem

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Though tetrapyrazinoporphyrazines (TPyzPzs) are generally presented as universal dark quenchers for oligonucleotide probes, the availability of TPyzPzs bearing different functional groups suitable for attachment to 3′, and 5′ ends or intrastrand positions remains rather limited. Therefore, a synthetic route to hexa(bis(2‐methoxyethyl)amino) or hexa(diethylamino) TPyzPzs functionalized by an azide, hydroxy, or carboxy group or their combinations was developed. Studies of self‐assembly into J‐dimers in nonpolar solvents and their stability upon titration with pyridine (association constants, KP values, ranging 0.32–12.7×102 M−1) revealed that smaller peripheral substituents and functionalization of TPyzPzs improves the stability of J‐dimers. ΦΔ and ΦF were low for the monomers (ΦF<0.0001, ΦΔ<0.008, DMF) due to quenching by intramolecular charge transfer; however, they increased in nonpolar solvents and after self‐assembly into J‐dimer (up to ΦF=0.027, ΦΔ=0.28).

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Syntheses of Octa(dialkylamino)azaphthalocyanines

Cited by 22 publications

References 7 publications

Tetraimidazophthalocyanines

Tetraimidazophthalocyanines

Clathrate Formation from Octaazaphthalocyanines Possessing Bulky Phenoxyl Substituents: A New Cubic Crystal Containing Solvent‐Filled, Nanoscale Voids

Synthesis and J‐Dimer Formation of Tetrapyrazinoporphyrazines with Different Functional Groups for Potential Biomolecular Probe Applications

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