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Synlett 2014; 25(15): 2127-2132
DOI: 10.1055/s-0034-1378524
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© Georg Thieme Verlag Stuttgart · New York

Synthesis, Photophysical, Electrochemical Properties and Charge-Transfer Complexation Studies of Piperazinophanes

Ayyavu Thirunarayanan
Department of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India   Fax: +91(44)22300488   eMail: perumalrajakumar@gmail.com
,
Perumal Rajakumar*
Department of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India   Fax: +91(44)22300488   eMail: perumalrajakumar@gmail.com
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Publikationsverlauf

Received: 16. April 2014

Accepted after revision: 20. Juni 2014

Publikationsdatum:
06. August 2014 (online)

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Abstract

Several 1:1 and 2:2 oligomeric forms of piperazinophanes with oxa–aza intraannular functionalities and containing various bicyclic ring systems as spacer units were prepared by a one-pot method under simple and mild conditions through a multicomponent reaction strategy involving a Mannich reaction. All the piperazinophanes exhibited absorption maxima in the range 242–356 nm and emission bands between 432 and 501 nm. The photophysical behaviors of the piperazinophanes and their binding properties for 7,7,8,8-tetracyanoquinodimethane, ethylene-1,1,2,2-tetracarbonitrile, and paraquat were examined.

Key words

supramolecular chemistry - photochemistry - host–guest systems - electrochemistry - cyclophanes

Supporting Information

    for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
  • Supporting Information
 

  • References and Notes

  • 1 Lehn J.-M. Science 1985; 227: 849
    CrossrefSuche in Google Scholar
  • 2 Schneider H.-J. Angew. Chem. Int. Ed. 2009; 48: 3924
    CrossrefSuche in Google Scholar
  • 3 Bhasikuttan AC, Pal H, Mohanty J. Chem. Commun. 2011; 47: 9959
    CrossrefSuche in Google Scholar
  • 4 Frampton MJ, Anderson HL. Angew. Chem. Int. Ed. 2007; 46: 1028
    CrossrefSuche in Google Scholar
  • 7 Ko YH, Kim E, Hwang I, Kim K. Chem. Commun. 2007; 1305
  • 8 Mohanty J, Nau WM. Angew. Chem. Int. Ed. 2005; 44: 3750
    CrossrefSuche in Google Scholar
  • 11 Dutta Choudhury S, Mohanty J, Pal H, Bhasikuttan AC. J. Am. Chem. Soc. 2010; 132: 1395
    CrossrefSuche in Google Scholar
    • 12a Ramasubbu A, Wainwright KP. J. Chem. Soc., Chem. Commun. 1982; 277
    • 12b Hancock RD, Dobson SM, Evers A, Wade PW, Ngwenya MP, Boeyens JC. A, Wainwright KP. J. Am. Chem. Soc. 1988; 110: 2788
      CrossrefSuche in Google Scholar
    • 12c Li YJ, Murase I, Reibenspies J, Martell AE. Inorg. Chim. Acta 1996; 246: 89
      CrossrefSuche in Google Scholar
    • 13a Love CS, Chechik V, Smith DK, Wilson K, Ashworth I, Brennan C. Chem. Commun. 2005; 1971
    • 13b Vemula PK, John G. Chem. Commun. 2006; 2218
    • 14a Claude S, Lehn J.-M, Schmidt F, Vigneron JP. J. Chem. Soc., Chem. Commun. 1991; 1182 ; corrigendum: J. Chem. Soc., Chem. Commun. 1991, 1656
    • 14b Čudić P, Žinić M, Tomišić V, Simeon V, Vigneron J.-P, Lehn J.-M. J. Chem. Soc., Chem. Commun. 1995; 1073
    • 14c Colquhoun HM, Greenland BW, Zhu Z, Shaw JS, Cardin CJ, Burattini S, Elliott JM, Basu S, Gasa TB, Stoddart JF. Org. Lett. 2009; 11: 5238
      CrossrefSuche in Google Scholar
    • 17a Bencini A, Bianchi A, Garcia-Espana E, Mangani S, Micheloni M, Orioli P, Paoletti P. Inorg. Chem. 1988; 27: 1104
      CrossrefSuche in Google Scholar
    • 17b Menif R, Martell AE. J. Chem. Soc., Chem. Commun. 1989; 1521
  • 18 Lehn J.-M. Angew. Chem. 1988; 100: 91 ; Angew. Chem., Int. Ed. Engl. 1988, 27, 90
    CrossrefSuche in Google Scholar
  • 20 Kimura E, Kuramoto Y, Koike T, Fijioka H, Kodama M. J. Org. Chem. 1990; 55: 42
    CrossrefSuche in Google Scholar
    • 22a Valks GC, McRobbie G, Lewis EA, Hubin TJ, Hunter TM, Sadler PJ, Pannecouque C, De Clercq E, Archibald SJ. J. Med. Chem. 2006; 49: 6162
      CrossrefSuche in Google Scholar
    • 22b Balakrishna MS, Suresh D, Rai A, Mague JT, Panda D. Inorg. Chem. 2010; 49: 8790
      CrossrefSuche in Google Scholar
    • 22c William AD, Lee AC.-H, Blanchard S, Poulsen A, Teo E, Nagaraj H, Tan E, Chen D, Williams M, Sun ET, Goh KC, Ong WC, Goh SK, Hart S, Jayaraman R, Pasha MK, Ethirajulu K, Wood JM, Dymock BW. J. Med. Chem. 2011; 54: 4638
      CrossrefSuche in Google Scholar
  • 27 Precyclophane Diynes 13–16; General Procedure A mixture of the appropriate dihydroxy compound 9–12 (0.5 g, 3.1 mmol), HC≡CCH2Br (0.61 mL 6.86 mmol), and K2CO3 (2.15 g 15.6 mmol) in DMF (15 mL) was stirred for 48 h at r.t. When the reaction was complete, the mixture was poured into H2O and extracted with CHCl3 (3 × 100 mL). The organic phases were combined, washed with brine (2 × 50 mL), dried (Na2SO4), and filtered. The solvent was evaporated in vacuo and the residue was purified by column chromatography [silica gel CHCl3–MeOH (9:1)]. 2,7-Bis(prop-2-yn-1-yloxy)naphthalene (13) Prepared from naphthalene-2,7-diol (9; 0.5 g, 3.1 mmol) as a white solid; yield: 0.41 g (82%); mp 194 °C; 1H NMR (300 MHz, CDCl3): δ = 2.56 (t, J = 2.4 Hz, 2 H); 4.79 (d, J = 2.1 Hz, 4 H); 7.04–7.07 (m, 4 H); 7.46 (d, J = 2.1 Hz, 2 H); 13C NMR (75 MHz, CDCl3): δ = 55.8, 75.7, 78.5, 107.0, 116.6, 125.1, 129.4, 135.4, 156.2; ESI-MS: m/z = 236 [M+]; Anal. Calcd for C16H12O2: C, 81.34; H, 5.12. Found: C, 81.43; H, 5.06. Piperazinophanes 1–6 A mixture of precyclophane diyne 13–16 (0.2 g, 3.98 mmol), piperazine (0.04 g, 3.98 mmol), HCHO (0.02 g, 7.96 mmol from 37–41% formalin solution), and CuCl (0.04 g, 3.98 mmol) in 1,4-dioxane (30 mL) was heated to 90 °C under N2 for 2 h. When the reaction was complete, the solvent was removed under reduced pressure. The residue was extracted with CHCl3 (3 × 100 mL), washed with H2O (2 × 100 mL) and brine (150 mL), and dried (Na2SO4). The solvent was removed and the crude product was purified by column chromatography [silica gel, CHCl3–MeOH (24:1)]. 2,15-Dioxa-7,10-diazatetracyclo[14,5,3,27,10,019,23]-hexacosa-1(22),16(24),17,19(23),20-pentaene-4,12-diyne (1) Prepared from diyne 13 (0.3 g, 1.27 mmol) as a white solid; yield: 31%; mp 160 °C (dec); 1H NMR: (300 MHz, CDCl3): δ = 2.51 (s, 8 H); 3.26 (s, 4 H); 4.86 (s, 4 H); 7.00–7.04 (m, 2 H); 7.47 (s, 2 H); 7.67 (d, J = 8.7 Hz, 2 H); 13C NMR: (75 MHz, CDCl3): δ = 46.8, 51.4, 56.2, 80.8, 84.3, 107.9, 117.7, 125.1, 129.2, 135.4, 156.1; ESI-MS: m/z = 346 [M+]; Anal. Calcd for C22H22N2O2: C, 76.28; N, 6.40; H, 8.09%. Found: C, 76.19; N, 6.36; H, 7.97%.
  • 28 Benesi HA, Hildebrand JH. J. Am. Chem. Soc. 1949; 71: 2703
    CrossrefSuche in Google Scholar