Photophysical Features of Phthalocyanines Metallocomplexes with Out-of-Plane Ligands

The objective of this work was synthesizing of Ti-, Zr-, Hf-phthalocyanines, containing chloride ions or dibenzoylmethanate fragments coordinated in out-of-plane positions to macrocycle. Spectroscopic and photophysical parameters of phthalocyanines metallocomplexes with metal atoms Ti(IV), Zr(IV) and Hf(IV) and spectroscopic features of Mg- and Zn-phthalocyanines have been detected and characterized at ambient and liquid nitrogen temperatures. The efficient intersystem crossing observed for Hf-phthalocyanine leads to very weak fluorescence and suppresses the fluorescence lifetimes to less than 1 ns. Changing of nature of central metals from heavy Hf(IV) atom to lighter atoms: Zr(IV), Zn(II), Ti(IV), Mg(II) lead to noticeable increasing of fluorescence lifetimes up to maximum value of 6,6 ns for Mg-phthalocyanine. At the same time the values of fluorescence quantum yield rises from 1 % for Hf-phthalocyanine to 56 % for Mg-phthalocyanine. The heavy atom effect has a substantially greater impact on photophysical parameters metallocomplexes of phthalocyanines than influence of attachment out-of-plane ligands.