Two kinds of substituted phthalocyaninatozinc, tetra-beta-phthalimidobutoxy phthalocyaninatozinc (1) and tetra-beta-phthalimidomethyl phthalocyaninatozinc (2), were synthesized by mix melting method, which bear the same phthalimide substituents but the linking of the substituents to the phthalocyanine ring is different. The substituent linking to the phthalocyanine ring is one methylene in ZnPc (2), while the substituents linking to the phthalocyanine ring is four methylenes and one ather in ZnPc (1), in which ather is near by phthalocyanine ring. The absorption and fluorescence spectra and the abilities of singlet oxygen generation of these two phthalocyanines were compared with respect to the effect of different linked fashions. The magnitude of the redshift of absorption and fluorescence spectra relative to unsubstituded ZnPc is greater for tetra-beta-phthalimidobutoxy phthalocyaninatozinc (1) than for tetra-beta-phthalimidomethyl phthalocyaninatozinc (2). This result is related to the presence of stronger electron donating peripheral substituents of ZnPc (1), with phiF of (1) is larger than that of (2) and the abilities of singlet oxygen generation of (1) is smaller than that of (2).
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Chem Asian J
November 2024
Department of Chemistry, Faculty of Science, Niigata University, Nishi-ku, Niigata, 950-2181, Japan.
Despite the significant development and extensive application of phthalocyanine and related azaporphyrins, little attention has been paid to meso-N-substituted azaporphyrinoids. Here, we report new derivatives of 5,10,20-triaryl-5,15-diazaporphyrinoids (ArDAP), which are reversibly redox-switchable between the 18π- and 19π-electron state. Four kinds of metal(II) complexes and free bases of ArDAP were prepared by metal-templated cyclization of metal(II) complexes of 5,10,15-triaryl-10-azabiladiene-ac with sodium azide or copper-catalyzed N-phenylation of 10,20-diaryl-5,15-diazaporphyrins (ArDAP) with diphenyliodonium hexafluorophosphate.
View Article and Find Full Text PDFJ Porphyr Phthalocyanines
November 2023
Department of Chemistry, The Johns Hopkins University, 3400N. Charles Street, Baltimore, Maryland 21218, USA.
A high-valent iron(IV)-oxo porphyrin radical cation (Fe(O)(porph) serves as a key, reactive intermediate for a range of heme enzymes, including cytochrome P450 (CYP), horseradish peroxidase (HRP), and catalase (CAT). Synthetic analogs of this intermediate, known as Compound-I (Cpd-I) in the heme enzyme literature, have been generated with different tetrapyrrolic, macrocyclic ligands, including porphyrin derivatives, and the closely related ring-contracted macrocycles, corroles and corrolazines. These synthetic analogs have been useful for assigning and understanding structural and spectroscopic features and examining the reactivity of Cpd-I-like species in controlled and well-defined environments.
View Article and Find Full Text PDFPhys Chem Chem Phys
July 2024
Thin Film and Nano Science Laboratory, Department of Physics, Jadavpur University, Kolkata 700 032, India.
Spatial self-phase modulation based on the optical Kerr effect has gained momentum in recent years to analyse the nonlinear optical properties of 2D inorganic nanomaterials. In the present work, we investigate the strong light-matter interaction of organic semiconducting materials based on SSPM, by developing Cu-phthalocyanine (CuPc) nanotubes a solvothermal technique. The low bandgap of CuPc facilitates the study of its nonlinear optical properties for a broad spectrum range from 671 nm to 405 nm.
View Article and Find Full Text PDFMolecules
April 2024
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China.
LiCO is the most tenacious parasitic solid-state product in lithium-air batteries (LABs). Developing suitable redox mediators (RMs) is an efficient way to address the LiCO issue, but only a few RMs have been investigated to date, and their mechanism of action also remains elusive. Herein, we investigate the effects of the central metal ion in binuclear metal phthalocyanines on the catalysis of LiCO decomposition, namely binuclear cobalt phthalocyanine (bi-CoPc) and binuclear cobalt manganese phthalocyanine (bi-CoMnPc).
View Article and Find Full Text PDFDalton Trans
April 2024
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
The μ-nitrido-bridged iron phthalocyanine homodimer is a potent molecule-based CH oxidation catalyst that can effectively oxidize chemically stable CH under mild reaction conditions in an acidic aqueous solution including an oxidant such as HO. The reactive intermediate is a high-valent iron-oxo species generated upon reaction with HO. However, a detailed comparison of the CH oxidation activity of the μ-nitrido-bridged iron phthalocyanine dimer with those of μ-nitrido-bridged iron porphyrinoid dimers containing one or two porphyrin ring(s) has not been yet reported, although porphyrins are the most important class of porphyrinoids.
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