3 years ago

Preparation and Optical and Electrochemical Properties of Phthalocyanines with Four or Eight Diphenylphosphino, Diphenylphosphineoxide, and Diphenylphosphinesulfide Groups

Satoshi Yamamoto, Satoshi Ogawa, Shiduko Nakajo, Nakao Kobayashi, Takeshi Kimura, Hiroki Muraoka
Several phthalocyanines (Pcs), where 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 tetrakis(diphenylphosphino)tetrachloroPc [Pc(PPh2)4Cl4, 11], while refluxing 3 in ethoxyethanol in the presence of DBU yielded octakis(diphenylphosphino)Pc [Pc(PPh2)8, 12]. The reactions of 11 with mCPBA or elemental sulfur produced tetrakis(diphenylphosphoryl)tetrachloroPc [Pc(POPh2)4Cl4, 13] or tetrakis(diphenylthiophosphinyl)tetrachloroPc [Pc(PSPh2)4Cl4, 15], respectively, while that of 12 with mCPBA or elemental sulfur afforded octakis(diphenylphosphoryl)Pc [Pc(POPh2)8, 14] or octakis(diphenylthiophosphinyl)Pc [Pc(PSPh2)8, 16], respectively. Octakis(diphenylphosphino)-octafluorophthalocyaninato magnesium [Pc(PPh2)8F8Mg, 17] was prepared from tetrafluorophthalonitrile (6) via 2 step reactions. The structures of simplified model compounds, 11a—16a, were optimized using the DFT method 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.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejoc.201701676

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