Synthesis and spectral properties of mixed-ligand Zr and Hf phthalocyanine complexes with out-of-plane coordinated alkylamino--ketoenolate chromophores and decanoate

The development of novel materials based on modification of phthalocyanines is promising for various applications in science, medicine and technology. Here mixed-ligand Zr and Hf phthalocyanine complexes with out-ofplane coordinated alkylamino-beta-ketoenolate chromophores and decanoate were synthesized for the first time. Complexes were obtained by one stage reaction of bis(decanoato)zirconium and hafnium phthalocyanines with alkylamino-beta-ketoenols that resulted in replacement of only one decanoate ligand with the alkylamino beta-ketoenol. Therefore, mixed-ligand Zr and Hf complexes with two chromophore systems (phthalocyanine and alkylamino-beta-ketoenol) were synthesized by using four different alkylamino-beta-ketoenols, and their structural characterizations were carried out by using some spectroscopic methods: H-1 NMR, UV-Vis, IR and MALDI TOF MS. In the UV-Vis spectra of the obtained complexes, the absorption bands characteristic for phthalocyanine system were observed along with additional absorption band of out-of-plane ligand (in the region 440-480 nm). The fluorescence spectra of investigated compounds are characterized by a maximum at about 690 nm, which corresponds to the emission of the phthalocyanine macrocycle, while the emission of alkylamino-beta-ketoenol ligand is not observed.