Preparation and Optical and Electrochemical Properties of Phthalocyanines with Four or Eight Diphenylphosphino, Diphenylphosphoryl, and Diphenylthiophosphinyl Groups

Preparation and Optical and Electrochemical Properties of Phthalocyanines with Four or Eight... 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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png European Journal of Organic Chemistry Wiley

Preparation and Optical and Electrochemical Properties of Phthalocyanines with Four or Eight Diphenylphosphino, Diphenylphosphoryl, and Diphenylthiophosphinyl Groups

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Publisher
Wiley Subscription Services, Inc., A Wiley Company
Copyright
© 2018 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
ISSN
1434-193X
eISSN
1099-0690
D.O.I.
10.1002/ejoc.201701676
Publisher site
See Article on Publisher Site

Abstract

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.

Journal

European Journal of Organic ChemistryWiley

Published: Jan 14, 2018

Keywords: ; ; ; ; ;

References

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