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

Abstract

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-of-plane coordinated alkylamino-β-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-β-ketoenols that resulted in replacement of only one decanoate ligand with the alkylamino-β-ketoenol. Therefore, mixed-ligand Zr and Hf complexes with two chromophore systems (phthalocyanine and alkylamino-β-ketoenol) were synthesized by using four different alkylamino-β-ketoenols, and their structural characterizations were carried out by using some spectroscopic methods: 1H 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-β-ketoenol ligand is not observed.