Synlett 2018; 29(13): 1693-1699
DOI: 10.1055/s-0037-1610186
letter
© Georg Thieme Verlag Stuttgart · New York

Dissymmetric Bay-Functionalized Perylenediimides

Kapil Kumar
a   Department of Chemistry, UGC Centre for Advanced Studies, Guru Nanak Dev University, Amritsar 143 005, India   Email: prabhpreet.chem@gndu.ac.in
,
Gaurav Bhargava
b   Department of Chemical Sciences, IK Gujral Punjab Technical University, Kapurthala-144601, Punjab, India
,
Subodh Kumar
a   Department of Chemistry, UGC Centre for Advanced Studies, Guru Nanak Dev University, Amritsar 143 005, India   Email: prabhpreet.chem@gndu.ac.in
,
Prabhpreet Singh  *
a   Department of Chemistry, UGC Centre for Advanced Studies, Guru Nanak Dev University, Amritsar 143 005, India   Email: prabhpreet.chem@gndu.ac.in
› Author AffiliationsThis work was supported by CSIR [02(0267)/16/EMR-II] and DST-SERB (EMR/2016/002239) grants.
Further Information

Publication History

Received: 29 March 2018

Accepted after revision: 17 May 2018

Publication Date:
20 June 2018 (online)

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Abstract

We report the synthesis of perylenediimide (PDI)-based ­donor–acceptor hybrids through dissymmetric bay functionalization of PDIs. The dissymmetric bay-functionalized di- and trisubstituted PDIs were characterized by using one- and two-dimensional NMR spectroscopy. Density functional theory calculations revealed (i) an energy gap between the HOMO and LUMO in the range 2.14–2.34 eV, beneficial for charge-transfer properties; and (ii) a twist angle between the two naphthalene units in the range 17–26°, which might be beneficial for disruption of co-facial stacking of the PDI.

Key words

perylenediimide - dissymmetric functionalization - bay functionalization - nitration - density functional theory

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610186.
  • Supporting Information
 

  • References and Notes

  • 1 Würthner F. Chem. Commun. 2004; 1564
    PubMed
  • 3 Huang C. Barlow S. Marder SR. J. Org. Chem. 2011; 76: 2386
    CrossrefPubMedSearch in Google Scholar
  • 7 Fernández-Lázaro F. Zink-Lorre N. Sastre-Santos A. J. Mater. Chem. A 2016; 4: 9336
    CrossrefSearch in Google Scholar
  • 8 Li G. Zhao Y. Li J. Cao J. Zhu J. Sun XW. Zhang Q. J. Org. Chem. 2015; 80: 196
    CrossrefPubMedSearch in Google Scholar
  • 9 Mende LS. Fechtenkötter A. Müllen K. Moons E. Frienda RH. MacKenzie JD. Science 2001; 293: 1119
    CrossrefPubMedSearch in Google Scholar
  • 24 Dissymmetric Trisubstituted PDI 2; Typical ProcedurePDI 9 (300 mg, 0.51 mmol) was dissolved in CH2Cl2 (30 mL). HNO3 (771.56 μL, 8.60 mmol), CAN (280 mg, 0.51 mmol), and H2SO4 (984.95 μL, 9.65 mmol) were added, and the mixture was stirred at r.t. for 10 h. When the reaction was complete (TLC), H2O was added to the mixture and the organic layer was repeatedly extracted with water (pH 7.0), dried (Na2SO4), and concentrated. The crude product was purified by column chromatography (silica gel, 70% CHCl3–hexane).
  • 25 PDI 2Dark-blue solid; yield: 316 mg (0.468 mmol, 91.3%); Rf = 0.40 (CHCl3–hexane, 7:3). IR (ATR): 3287, 2966, 2933, 2875, 2360, 2126, 1701, 1661, 1595, 1543, 1459, 1411, 1357, 1313, 1250, 1200, 1070, 999, 928, 809 cm–1. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 9.12 (s, 1 H, perylene ArH), 8.85 (s, 1 H, perylene ArH), 8.55 (d, J = 8.0 Hz, 1 H, perylene ArH), 8.53 (s, 1 H, perylene ArH), 8.30 (d, J = 8.0 Hz, 1 H, perylene ArH), 5.07 (d, J = 2.0 Hz, 2 H, OCH2), 5.01–5.06 (m, 2 H, ethylpropyl), 2.69 (t, J = 2.5 Hz, 1 H, –C≡H), 2.21–2.27 (m, 4 H, ethylpropyl), 1.92–1.98 (m, 4 H, ethylpropyl), 0.91 (t, J = 7.5 Hz, 6 H, ethylpropyl), 0.94 (t, J = 7.5 Hz, 6 H, ethylpropyl). 13C NMR (125 MHz, CDCl3, 25 °C): δ = 11.23, 11.35, 24.84, 25.03, 56.92, 58.35, 58.60, 75.76, 78.60, 116.31, 123.77, 126.68, 127.10, 127.44, 128.11, 129.56, 129.75, 148.07, 148.61, 157.79. Emission = 536 nm; Absorption = 561 nm (MeCN–H2O with f w = 50 vol%).
  • 26 Dissymmetric Disubstituted PDI 1; General ProcedurePDI 9 (50 mg, 0.085 mmol) was dissolved in CH2Cl2 (5 mL). HNO3 (42.86 μL, 0.48 mmol), CAN (22.22 mg, 0.04 mmol), and H2SO4 (22.80 μL, 0.21 mmol) were added, and the mixture was stirred at r.t. for 4 h. When the reaction was complete (TLC), H2O was added to the mixture and the organic layer was repeatedly extracted with H2O (pH 7.0), dried (Na2SO4), and concentrated. The crude product was purified by column chromatography (silica gel, 70% CHCl3–hexane).
  • 27 PDI 1Dark-purple solid; yield: 48.2 mg (0.076 mmol, 89.6%); Rf = 0.26 (CHCl3–hexane, 7:3); IR (ATR): 3265, 2924, 2853, 2361, 1699, 1659, 1594, 1461, 1412, 1315, 1251, 1070, 808, 743 cm–1. 1H NMR (500 MHz, CDCl3, 25 °C): δ = 9.05 (s, 1 H, perylene ArH), 8.78 (d, J = 8.0 Hz, 1 H, perylene ArH), 8.68 (d, J = 8.0 Hz, 1 H, perylene ArH), 8.64 (d, J = 8.0 Hz, 2 H, perylene ArH), 8.51 (s, 1 H, perylene ArH), 5.06–5.10 (m, 2 H, ethylpropyl), 5.05 (d, J = 2 Hz, 2 H, OCH2), 2.66 (t, J = 2.5 Hz, 1 H, –C≡H), 2.21–2.30 (m, 4 H, ethylpropyl), 1.90–1.99 (m, 4 H, ethylpropyl), 0.90–0.95 (m, 12 H, ethylpropyl). 13C NMR (125 MHz, CDCl3, 25 ºC): δ = 11.28, 11.35, 24.93, 25.04, 56.64, 58.05, 58.09, 76.14, 78.17, 117.84, 123.43, 124.30, 124.76, 126.88, 128.08, 128.45, 129.67, 132.15, 135.41, 148.04, 156.62. Emission = 542 nm; Absorption = 560 nm (MeCN–H2O with f w = 50 vol%).
  • 28 PDI 3Dark-purple solid; yield: 50.7 mg (0.078 mmol, 94.3%); Rf = 0.20 (CHCl3–hexane, 7:3). IR (ATR): 3453, 3301, 2964, 2874, 2360, 1698, 1658, 1593, 1537, 1460, 1415, 1314, 1264, 1201, 1071, 988, 850, 809, 744 cm–1. 1H NMR (400 MHz, CDCl3, 25 °C): δ = 9.08 (s, 1 H, perylene ArH), 8.79 (d, J = 9.6 Hz, 1 H, perylene ArH), 8.60–8.72 (m, 3 H, perylene ArH), 8.36 (s, 1 H, perylene ArH), 5.03–5.11 (m, 2 H, ethylpropyl), 4.49 (t, J = 9.6 Hz, 2 H, –OCH2), 2.81 (td, J = 9.6, 3.2 Hz, 2 H, –CH2), 2.19–2.34 (m, 4 H, ethylpropyl), 1.87–2.01 (m, 5 H, merged –CH + ethylpropyl), 0.90–0.96 (m, 12 H, ethylpropyl). 13C NMR (125 MHz, CDCl3): δ = 11.26, 11.28, 24.89, 25.01, 29.71, 57.94, 58.08, 58.23, 58.38, 128.83, 129.00, 129.55, 129.82, 131.29, 131.54, 141.03, 147.65, 147.82. Emission = 540 nm; Absorption = 550 nm (MeCN–H2O with f w = 50 vol%).
  • 29 PDI 4Dark-blue solid; yield: 54.2 mg (0.079 mmol, 94.3%); Rf = 0.27 (CHCl3–hexane, 7:3). IR (ATR): 3452, 3301, 3061, 2961, 2926, 2873, 2360, 1702, 1662, 1597, 1541, 1459, 1419, 1344, 1314, 1268, 1201, 1073, 1004, 926, 810, 742, 652 cm–1. 1H NMR (400 MHz, CDCl3, 25 °C): δ = 9.15 (s, 1 H, perylene ArH), 8.85 (s, 1 H, perylene ArH), 8.54 (d, J = 8.0 Hz, 1 H, perylene ArH), 8.39 (s, 1 H, perylene ArH), 8.30 (d, J = 8.0 Hz, 1 H, perylene ArH), 5.00–5.10 (m, 2 H, ethylpropyl), 4.53 (t, J = 7.2 Hz, 2 H, –OCH2), 2.81 (td, J = 7.2, 2.4 Hz, 2 H, –CH2), 2.19–2.30 (m, 4 H, ethylpropyl), 1.99 (t, J = 2.8 Hz, 1 H, –CH), 1.89–1.98 (m, 4 H, ethylpropyl), 0.90–0.95 (m, 12 H, ethylpropyl). 13C NMR (125 MHz, CDCl3): δ = 11.26, 11.32, 18.94, 24.86, 25.04, 58.36, 58.63, 68.04, 71.02, 78.76, 116.01, 123.54, 126.60, 127.53, 129.64, 129.80, 148.03, 159.02. Emission = 541 nm; Absorption = 565 nm (MeCN–H2O with f w = 50 vol%).
  • 30 PDI 5Brownish-red liquid; yield: 102.1 mg (0.15 mmol, 95.2%); Rf = 0.23 (CHCl3–hexane, 7:3). 1H NMR (500 MHz, CDCl3, 25 °C): δ = 10.15 (s, 1 H, CHO), 8.82 (s, 1 H, perylene ArH), 8.66 (t, J = 10.0 Hz, 2 H, perylene ArH), 8.24 (d, J = 10.0 Hz, 2 H, perylene-ArH), 8.06 (d, J = 10.0 Hz, 2 H, ArH), 7.82 (d, J = 10.0 Hz, 1 H, perylene ArH), 7.74 (d, J = 10.0 Hz, 1 H, ArH), 7.66 (d, J = 10.0 Hz, 1 H, ArH), 5.01–5.06 (m, 2 H, ethylpropyl), 2.19–2.28 (m, 4 H, ethylpropyl), 1.88–1.96 (m, 4 H, ethylpropyl), 0.87–0.94 (m, 12 H, ethylpropyl). 13C NMR (125 MHz, CDCl3): δ = 191.2, 147.9, 147.7, 141.0, 136.4, 134.9, 131.6, 131.3, 129.9, 129.6, 129.0, 128.9, 128.1, 58.4, 58.3, 58.1, 58.0, 36.9, 29.7, 25.0, 24.9, 19.2, 11.3, 11.3.
  • 31 Mishra A. Nayak PK. Ray D. Patankar MP. Narasimhan KL. Periasamy N. Tetrahedron Lett. 2006; 47: 4715
    CrossrefSearch in Google Scholar