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Naphthalocyanines (Nc) attract special attention as π-extended phthalocyanine (Pc) derivatives with absorbance in the near IR range, which affords their application as PDT sensitizers, NIR imaging agents, materials for optoelectronics, nonlinear optics, etc. However, Ncs also have high tendency to aggregation, which leads to low solubility in common organic solvents as well as loss of luminescence and singlet oxygen generation. Their aggregation could be suppressed to some extent by the increase of temperature. However, the best way to obtain these complexes in the monomeric state is the supramolecular approach. The resulting monomeric forms of crown-Ncs were found to generate singlet oxygen; however, this process is also responsible for the particular photosensitivity of these compounds and their fast photodecomposition.