Synthesis and characterization of octa-alkyl-substituted metallophthalocyanines and noncentrosymmetrical metallophthalocyanines

Octylthio and octylsulfonyl metallophthalocyanines (MPcs) [M: Ni, Cu, Co, and Zn] were synthesized and characterized by spectroscopic, magnetic, and electrochemical measurements. The overall B and Q bands of octylsufonyl MPcs are blue-shifted, compared to octylthio MPcs due to electron attracting octylsulfonyl groups in the UV-Vis spectrum. In each series of octylthio and octylsulfonyl MPcs, the B (Soret) and Q band of NiPc are more blue-shifted than the other MPcs due to stronger electronegativity of the nickel central metal ion. Octylthio ZnPc gives the highest intensity of emission spectrum.; Octylthio NiPc and CoPc crystals are fibrous needles which are unsuitable for X-ray single crystal diffraction.; The broad EPR signal was observed in CuPc and CoPc because of the paramagnetic properties of central metal ions. The g value of octylthio CoPc increases with decreasing temperature due to more efficient spin-orbital coupling of the unpaired electron at lower temperature.; The redox potentials of MPcs were investigated by using cyclic voltammetry. All samples show quasi-reversible or irreversible voltammograms. Consequently, Δredox of octylsulfonyl MPcs does not present consistent increase, as expected, compared to Δredox of octylthio MPcs in contrast to the blue shift of the Q band in most octylsulfonyl MPcs, compared to octylthio MPcs in UV Vis spectrum.; In the second part of the thesis, we prepared a non-centrosymmetrical NiPc containing one triazole subunit and its complex with silver ions. The B (Soret) and Q band of silver dimer complex were blue-shifted against NiPc due to the electron-withdrawing effect of silver metal ions in the UV-Vis spectrum. FT IR spectroscopy was rather insensitive to NO3 − counter ions. Atomic Absorption Spectroscopy (AAS) showed a 10% of silver content in the sample solution. This is in fair agreement with a 7% silver content in the dimer complex.; In the third part of the thesis, we prepared a non-centrosymmetrical ZnPc containing one phenanthroline subunit. The B (Soret) band is seen around 360 nm and is red-shifted, compared to other metallophthalocyanines due to the extended π systems.