Multi-(phenylthio)porphyrinato Ni(II) compounds: Synthesis, structures and properties

A series of multi-(phenylthio)porphyrinato Ni(II) compounds were synthesized without the participation of transition metal catalysts. All of these products were well characterized by 1H NMR, 13C NMR and HRMS. Structures of three typical compounds were further confirmed by X-ray single crystal diffraction. Remarkable red shifts were observed in UV–vis absorption spectra of multi-(phenylthio)porphyrinato Ni(II) compounds which meet well with the electrochemical data. DFT calculation indicates that the phenylthio groups have strong effects on the frontier orbitals of these molecules. The order of a1u-like and a2u-like orbitals mainly distributed in porphyrin moiety is often inversed in energy when multi-phenylthio groups are attached.