Bulky-substituted phthalodinitriles and cobalt and copper phthalocyanines based on them: synthesis, thermal analysis and spectroscopic properties

Abstract

By the nucleophilic substitution of the nitro group in 4-nitrophthalononitrile for the residues of alkoxy-substituted phenols, the synthesis of alkoxyphenoxyphthalonitriles was carried out. By template condensation of the substituted phthalonitriles obtained with copper and cobalt acetates at 200 °C, the corresponding phthalocyaninates were obtained. The conditions for the isolation and purification of the complexes synthesized were selected. The stability of substituted phthalonitriles and phthalocyaninates synthesized based on them regarding to heating in an argon-oxygen medium was evaluated (1:1 ratio). It was found the compounds obtained are thermally stable, and the destruction of phthalocyanines begins at lower temperatures compared to the corresponding phthalonitriles. For the complexes synthesized, the spectroscopic properties in organic solvents and concentrated sulfuric acid were studied. The influence of the nature of the substituent, metal complexing agent and solvent on the nature of the spectroscopic curves and the position of the main absorption band of phthalocyanine complexes has been established. It is noted passing from polar aprotic solvents to nonpolar ones, a shift of the maximum of the Q absorption band for the studied macrocycles was observed. Electronic absorption spectra in sulfuric acid show a significant bathochromic shift of the absorption band. An increase in the length of the alkyl substituent practically was found not to affect the position of the absorption maximum. Passing from complexes with Co(II) to Cu(II), a bathochromic shift of the absorption maximum was observed.

Fluorinated- and non-fluorinated-diarylamine-Zn(ii) and Cu(ii) phthalocyanines as symmetrical vs. asymmetrical hole selective materials

“…It is well known that non-covalent interactions between two or more phthalocyanine (Pcs) molecules cause their derivatives to aggregate, leading to their low solubility in the majority of solvents. 37,38 We observed that Cu-based Pcs give poor solubility and make clusters with time in chlorobenzene, a solvent used for device fabrication. Thus, the likely cause of the PV underperformance seen in some MPcs could be attributed to a lesser degree of solubility and the molecular accumulation that prevent the efficient energetic coupling and introduce recombination centers, thus responsible for the lower PCE measured for PSCs.…”

Chemistry of Liquid Systems and Functional Materials Based on Coordination Compounds of Linear and Cyclic Polypyrroles

“…В этой связи разработка подходов к синтезу таких соединений является ключевым направлением химии металлофталоцианинов и перспективных материалов на их основе [96]. Металлокомплексы фталоцианинов магния, кобальта, меди и цинка получают путем сплавления соответствующего нитрила с солью металла (схема 5) [97][98][99][100][101][102][103][104][105][106][107].…”

Polyurethane-Based Photo/Thermal Energy-Storage Capsules Made with Manganese Phtalocyanine as a Photothermal Agent

“…Phthalocyanine has strong absorption in the red light region and good photothermal stability, and it is a good photothermal conversion material. 26,27 The absorption band of phthalocyanine can be further red-shifted to the near-infrared region by structural modifications, which benefits its further application. 28 Manganese phthalocyanine has strong light absorption in the near-infrared region and high photothermal conversion efficiency.…”

“…Carbon-based nanomaterials such as graphene and carbon nanotubes are the third type. − Efficient photothermal materials are the ones which have strong absorption, high photothermal conversion efficiency, and good light stability. , Phthalocyanine is a kind of functional compound having a large conjugated system with 18 π electrons in plane. Phthalocyanine has strong absorption in the red light region and good photothermal stability, and it is a good photothermal conversion material. , The absorption band of phthalocyanine can be further red-shifted to the near-infrared region by structural modifications, which benefits its further application . Manganese phthalocyanine has strong light absorption in the near-infrared region and high photothermal conversion efficiency. , Due to the planar structure of phthalocyanine, it may have little negative effect on the performance of phase change material when these two are mixed together in the core of the microcapsules.…”