Synthesis and spectral and thermal characterization of new metal-free and metallophthalocyanines: investigation of their photophysical, photochemical, and thin film properties

Novel tetrasubstituted metal-free (2), zinc (II) (3), cobalt (II) (4), and copper (II) (5) phthalocyanines bearing 2-phenylethanolate groups on the peripheral positions were synthesized by the cyclotetramerization reaction of the phthalonitrile derivative 1. The new compounds were characterized by a combination of IR, 1H NMR, 13C NMR, UV-Vis, elemental analysis, and MS spectra data. The thermal stabilities of the phthalocyanine compounds were determined by thermogravimetric analysis. For metal-free (2) and zinc (3) phthalocyanines, photochemical (photodegradation and singlet oxygen quantum yields) and photophysical (fluorescence quantum yields and fluorescence lifetimes) properties were analyzed in dimethylsulfoxide (DMSO). The cobalt (4) and copper (5) phthalocyanines were not evaluated for this purpose because of their paramagnetic behavior. The metal-free (2) and zinc (3) phthalocyanines' fluorescence quenching behaviors were also investigated. The new phthalocyanine compounds' fluorescence emissions were effectively quenched by 1,4-benzoquinone in DMSO. The thin films of the cobalt phthalocyanine compound (4) were grown by electron beam evaporation technique. Crystalline CoPc (4) thin films were investigated by X-ray diffraction spectroscopy. Surface morphology of the CoPc (4) thin films was characterized by SEM.