Several phthalocyanines (Pcs), in which four or eight phosphines are directly linked to their periphery, have been prepared. The starting materials, 4‐(diphenylphosphino)‐5‐chlorophthalonitrile (2), 4,5‐bis(diphenylphosphino)phthalonitrile (3), and 4‐(diphenylphosphino)‐5‐(diphenylphosphoryl)‐phthalonitrile (4), were prepared by the reaction of 4,5‐dichlorophthalonitrile (1) and diphenyltrimethylsilylphosphine in toluene at 110 °C. Compound 2 was treated with Li in hexan‐1‐ol at 120 °C, to produce β‐tetrakis(diphenylphosphino)tetrachloroPc [Pc(PPh2)4Cl4, 11], while refluxing 3 in ethoxyethanol in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) yielded β‐octakis(diphenylphosphino)Pc [Pc(PPh2)8, 12]. The reactions of 11 with mCPBA or elemental sulfur produced β‐tetrakis(diphenylphosphoryl)tetrachloroPc [Pc(POPh2)4Cl4, 13] or β‐tetrakis(diphenylthiophosphinyl)tetrachloroPc [Pc(PSPh2)4Cl4, 15], respectively, whereas that of 12 with mCPBA or elemental sulfur afforded β‐octakis(diphenylphosphoryl)Pc [Pc(POPh2)8, 14] or β‐octakis(diphenylthiophosphinyl)Pc [Pc(PSPh2)8, 16], respectively. β‐Octakis(diphenylphosphino)‐α‐octafluorophthalocyaninato magnesium [Pc(PPh2)8F8Mg, 17] was prepared from tetrafluorophthalonitrile (6) in two‐step reactions. The structures of simplified model compounds 11a–16a were optimized using DFT methods with the Gaussian 09 program. The optimized structures were utilized to calculate the HOMO and LUMO orbital energies, and the electronic transitions in the absorption spectra by the TD‐DFT method.
European Journal of Organic Chemistry – Wiley
Published: Jan 14, 2018
Keywords: ; ; ; ; ;
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