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

Loading next page...
 
/lp/wiley/preparation-and-optical-and-electrochemical-properties-of-vApfHV0Xk8
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

You’re reading a free preview. Subscribe to read the entire article.


DeepDyve is your
personal research library

It’s your single place to instantly
discover and read the research
that matters to you.

Enjoy affordable access to
over 18 million articles from more than
15,000 peer-reviewed journals.

All for just $49/month

Explore the DeepDyve Library

Search

Query the DeepDyve database, plus search all of PubMed and Google Scholar seamlessly

Organize

Save any article or search result from DeepDyve, PubMed, and Google Scholar... all in one place.

Access

Get unlimited, online access to over 18 million full-text articles from more than 15,000 scientific journals.

Your journals are on DeepDyve

Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.

All the latest content is available, no embargo periods.

See the journals in your area

DeepDyve

Freelancer

DeepDyve

Pro

Price

FREE

$49/month
$360/year

Save searches from
Google Scholar,
PubMed

Create lists to
organize your research

Export lists, citations

Read DeepDyve articles

Abstract access only

Unlimited access to over
18 million full-text articles

Print

20 pages / month

PDF Discount

20% off