A series of novel phenyl-substituted planar and sandwich-type complexes of Eu, Er and Lu with phthalo and naphthalocyanine ligands was obtained. A successful synthesis of dinaphthalocyanines from the ligand is described. A selective synthetic approach to the phenyl-substituted triphthalocyanine complexes from the ligand and acetylacetonate salts of lanthanides was developed. Correlations between the ionic radii of the central metal and absorption maxima were obtained for sandwich-type complexes. It was found that intervalence (IV) bands for dinaphthalocyanine complexes were red-shifted about 200 nm in comparison with corresponding diphthalocyanines, reaching 1797 nm for the Eu complex. The electrochemical behaviour of planar and sandwich-type Lu complexes was investigated. For the first time a spectroelectrochemical study of multistep reduction and oxidation processes for a triple-decker complex was carried out using the example of the triphthalocyanine of Lu. The structures of the compounds obtained were determined by ¹H NMR and high resolution MALDI TOF/TOF. The first single-crystal structure for an aryl-substituted double-decker complex was described using the example of the diphthalocyanine of Lu, showing the presence of intramolecular π–π interactions between phenyl groups.

Herein, we present an overview of the approaches for the synthesis of phthalocyanines bearing electron-withdrawing halogen-, nitro- and N-substituted imide functional groups in different positions of the phthalocyanine macrocycle. Some approaches for synthesis of the corresponding substituted phthalonitriles are also covered. This review includes unusual techniques for the synthesis of phthalocyanines, such as microwave-assisted approaches, synthesis in ionic liquids and synthesis under mild conditions based on the double-addition of oximes. The synthesis and optical and magnetic peculiarities of the surprisingly stable anionic forms of double-decker phthalocyanine complexes with electron-withdrawing substituents are also highlighted. Finally, the various applications of phthalocyanines with electron-withdrawing functional groups (optical limiters, gas sensors, organic thin-film transistors, memory elements, single-molecule magnets, and medicinal chemistry) and the preparation of hybrid nanoparticles coated with a phthalocyanine shell are discussed.

Novel heteroleptic naphthalo-phthalocyaninates of lutetium possessing a symmetrical substituted naphthalocyanine deck were synthesized on the basis of two preformed synthetic blocks: naphthalocyanine ligand and lutetium phthalocyaninates. The compounds obtained were characterized by ¹H NMR and high-resolution MALDI-TOF/TOF mass spectrometry. The correlation between the nature of the substituents and the spectral properties of the target complexes was determined by the introduction of electron-donating (aryl-, aryloxy-) or electron-withdrawing (chloro-) substituents into the phthalocyanine deck. In addition, the nature of peripheral substituents was shown not to affect drastically the phthalocyanine conductivity and activation energy. Conductivity properties depend on thin film morphology which, in turn, relies on intermolecular π–π interactions.

Phenyl-substituted zinc naphthalocyaninate forms amorphous floating layers at the air/water interface. Floating monolayers are generated when the area per one molecule value (A_mol) lying between 1.90 and 0.97 nm². When A_mol ≤ 0.97 nm², amorphous bilayers are formed.