Synthesis of new axial coordinated water
dissolved phthalocyanine complexes of titanium, zirconium and hafnium.
Tomachynski L.A., Chernii V.Ya.
and Volkov S.V.
Institute of General and Inorganic
03680 Palladina ave 32/34 Kyiv, Ukraine.
The introduction of axial coordinated ligands to the central atom
of metal has a strong influence on p -electron conjugation of the
macromolecule. In particular, axial substitution will have
several effect: i) it can alter the electronic structure of the
phthalocyanine; ii) it can bring in a dipole moment perpendicular
to the macrocycle plane; iii) it can vary the spatial
relationships between neighbouring molecules via steric effects
and thus the magnitude of the intermolecular interactions. Large
axial coordinated ligands are able to alter the packing of the
molecules in the solid state and the tendency to aggregate in
Each of these effects can influence the photo conductive and
non-liner optical properties.
The aim of our current research is the synthesis of axial
substituted phthalocyaninato metal complexes, where the metal is
titanium (IV), zirconium (IV) and hafnium (IV), on the one hand
that have sufficient solubility in water, on the other hand they
potentially possess photo conductive and non-liner optical
Phthalocyaninato titanium (IV), zirconium (IV) and hafnium (IV)
complexes which contain gallic,
1,8-dihydroxynaphthalene-3,6-disulfonic (chromotropic), and
5-sulfosalicylic acids, as axial coordinated ligands were
obtained (Figure 1).
Chemical composition of all prepared complexes is confirmed by
data 1H NMR and IR spectroscopy, and results of
This ligands were chosen so as to alter both the spatial and
electronic properties of the materials, and contain groups that
provide solubility in water. Compared with the chloro ligands,
these substituents introduce steric crowding that give to form
aggregates in water, but on the other hand the tendency to form
aggregate reduces in case of transition to aprotonic solvent
(DMSO). Data of UV/vis spectra confirm it (Figure 2, 3).
In conclusion stable axial coordinated, water dissolved
phthalocyaninato titanium (IV), zirconium (IV) and hafnium (IV)
complexes were prepared. Studies on the photo conductive and
non-linear optical properties are in progress.
Figure 1. Synthesis of water
dissolved phthalocyaninato metal complexes.
Figure 2. Typical UV/vis spectra
of obtained compounds 1) in water, 2) in DMSO.
Figure 3. Suggesting structure of
the formed dimer in water solution.