Synthesis, spectroscopic, and electronic properties of new tetrapyrazinoporphyrazines with eight peripheral 2,6-diisopropylphenol groups

Metal-free, magnesium, titanyl, and vanadyl tetrapyrazinoporphyrazines substituted with eight 2,6-diisopropylphenoxy groups at the peripheral positions were prepared and characterized by NMR, UV-Vis, magnetic circular dichroism (MCD), and mass spectrometry methods. In addition, the Pc(2,6iPrPhO)8VO complex was characterized by EPR spectroscopy and X-ray crystallography. Reaction between TiCl4 with 4,5-(2,6-diisopropylphenoxy)phthalonitrile in N,N-dimethylaminoethanol resulted in the formation of a red open-chain trimer, which was characterized by mass spectrometry and X-ray crystallography. Electronic structures of new compounds and their excited state properties were probed by Density Functional Theory (DFT) and Time-Dependent DFT (TDDFT) methods.