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Synthesis 2002(9): 1245-1255
DOI: 10.1055/s-2002-32532
PAPER
© Georg Thieme Verlag Stuttgart · New York

Strategies for the Synthesis of ‘Through-Space’ Chromophore Dimers Based on [2.2]Paracyclophane

Glenn P. Bartholomew, Guillermo C. Bazan*
University of California: Santa Barbara, Department of Chemistry and Biochemistry, Department of Materials Engineering, Institute for Polymers and Organic Solids, Santa Barbara, California 93106, USA
Fax: +1(805)8934120; e-Mail: bazan@chem.ucsb.edu or bartholomew@chem.ucsb.edu;
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Publication History

Received 11 March 2002
Publication Date:
28 June 2002 (online)

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Abstract

The evolution and motivation of regiospecific synthetic protocols for 4,7,12,15- donor and/or acceptor substitution of [2.2]paracyclophane is described. Analysis of protocols for the creation of molecules that model interchromophore contacts and delocalization from multiply brominated [2.2]paracyclophane is provided. Substrates that allow for Horner-Emmons coupling as an entry to high yield procedures for synthesizing chromophores built around tetrasubstituted [2.2]paracyclophane are described. Additionally, the synthesis of precursors for site-specific coupling and the resulting products of donor and acceptor substitution are presented. Brief representative examples of the unusual spectroscopic properties of the target compounds are given.

Key words

[2.2]paracyclophanes - through-space chromophore - Horner-Emmons reaction - site-specific coupling - donor/acceptor substitution

    References

  • 1a Garnier F. Acc. Chem. Res.  1999,  32:  209 
    Google Scholar
  • 1b Servet B. Horowitz G. Ries S. Lagorsse O. Alnot P. Yassar A. Deloffre F. Srivastava P. Hajilaoui R. Lang P. Garnier F. Chem. Mater.  1994,  6:  1809 
    Google Scholar
  • 1c Dodalabalapur A. Torsi L. Katz HE. Science  1995,  268:  270 
    Google Scholar
  • The status of the field is well summarized in:
  • 2a Nguyen T.-C. Martini IB. Liu J. Schwartz BJJ. Phys. Chem. B  2000,  104:  237 
    CrossrefGoogle Scholar
  • 2b Conwell E. Trends in Polymer Sci.  1997,  5:  218 
    CrossrefGoogle Scholar
  • 2c Cornil J. dos Santos DA. Crispin X. Silbey R. Bredas JL. J. Am. Chem. Soc.  1998,  120:  1289 
    CrossrefGoogle Scholar
  • 3a Lee CH. Yu G. Moses AJ. Synth. Met.  1995,  69:  429 
    CrossrefGoogle Scholar
  • 3b Gettinger CL. Heeger AJ. Drake JM. Pine DJ. J. Chem. Phys.  1994,  101:  1673 
    CrossrefGoogle Scholar
  • 3c Kohler A. Gruner J. Friend RH. Mullen K. Scherf I. Chem. Phys. Lett.  1995,  243:  456 
    CrossrefGoogle Scholar
  • 4 Sheats JR. Barbara PF. Acc. Chem. Res.  1999,  32:  191 
    CrossrefGoogle Scholar
  • 5 Goldhaber-Gordon D. Montemerlo MS. Love C. Opiteck GJ. Ellenbogen JC. Proc. IEEE  1997,  85:  521 
    CrossrefGoogle Scholar
  • 6 Nespurek S. Sworakowski J. IEEE Eng. Medicine Bio.  1994,  13:  45 
    Google Scholar
  • 7 Joachim C. Gimzewski J. Chem. Phys. Lett.  1997,  265:  353 
    CrossrefGoogle Scholar
  • 8 Birge JJ. Amer. Sci.  1994,  348 
    Google Scholar
  • 9 Nanotechnology: Research and Perspectives   Cradall BC. Lewis J. MIT Press; Cambridge MA: 1992. 
    Google Scholar
  • 10 Fox MA. Acc. Chem. Res.  1999,  32:  201 
    CrossrefGoogle Scholar
  • 12 Guillet J. Polymer Photophysics and Photochemistry   Cambridge University Press; Cambridge UK: 1985. 
    Google Scholar
  • 13a Tretiak S. Zhang WM. Chernyak V. Mukamel S. Proc. Nat. Acad. Science U.S.A.  1999,  96:  13003 
    Google Scholar
  • 13b Strickler SJ. Cormier RA. Connolly JS. Int. J. Quantum Chem.  1991,  39:  345 
    Google Scholar
  • 13c Scholes GD. Ghiggino KP. Oliver AM. Paddon-Row MN. J. Am. Chem. Soc.  1993,  115:  4345 
    Google Scholar
  • 13d Clayton AHA. Scholes GD. Ghiggino KP. Paddon-Row MN. J. Phys. Chem.  1996,  100:  10912 
    Google Scholar
  • 14 Bartholomew GP. Bazan GC. Acc. Chem. Res.  2001,  34:  30 
    CrossrefGoogle Scholar
  • Chromophores studied in this manner include:
  • 15a Phenanthrenophane: Schweitzer D. Hausser KH. Haenel M. Chem. Phys.  1978,  29:  181 
    CrossrefGoogle Scholar
  • 15b Anthraceno-phane: Ishikawa S. Nakamura J. Iwata S. Sumitami M. Nagakura S. Sakata Y. Misumi S. Bull. Chem. Soc. Jpn.  1979,  52:  1346 
    CrossrefGoogle Scholar
  • 15c Fluorenophane: Haenel MW. Tetrahedron Lett.  1976,  3121 
    CrossrefGoogle Scholar
  • 15d Colpa JP. Hausser KH. Schweitzer D. Chem. Phys.  1978,  29:  187 
    CrossrefGoogle Scholar
  • 15e Pyrenophane and several isomers of naphthalenophane: Haenel M. Staab HA. Chem. Ber.  1973,  106:  2190 
    CrossrefGoogle Scholar
  • 15f Otsubo T. Mizogami S. Osaka N. Sakata Y. Misumi S. Bull. Chem. Soc. Jpn.  1977,  50:  1858 
    CrossrefGoogle Scholar
  • 15g Stilbenophanes: Anger I. Sandros K. Sundahl M. Wennerström O. J. Phys. Chem.  1993,  97:  1920 
    CrossrefGoogle Scholar
  • 15h Tsuge A. Nishimoto T. Uchida T. Yasutake M. Moriguchi T. Sakata K. J. Org. Chem.  1999,  64:  7246 
    CrossrefGoogle Scholar
  • For studies of cycloaddition reactions, see:
  • 16a Grieving H. Hopf H. Jones PG. Bubenitscheck P. Desvergne JP. Bouass-Laurent J. J. Chem. Soc., Chem. Commun.  1994,  1075 
    Google Scholar
  • 16b Okada Y. Ishii F. Akiyama I. Nishimura J. Chem. Lett.  1992,  1579 
    Google Scholar
  • 16c Grieving H. Hopf H. Jones PG. Bubenitscheck P. Desvergne JP. Bouass-Laurent J. Liebigs. Ann. Chem.  1995,  1949 
    Google Scholar
  • 17 Reichbartholomew GP. Bazan GC. J. Am. Chem. Soc.  2002,  124:  5183 
    CrossrefGoogle Scholar
  • 18 Reich HJ. Cram DJ. J. Am. Chem. Soc.  1969,  91:  3527 
    CrossrefGoogle Scholar
  • 19 Bazan GC. Oldham WJ. Lachicotte RJ. Tretiak S. Chernyak V. Mukamel S. J. Am. Chem. Soc.  1998,  120:  9188 
    CrossrefGoogle Scholar
  • 20 König B. Knieriem B. de Meijere A. Chem. Ber.  1993,  126:  1643 
    CrossrefGoogle Scholar
  • 21 Wang S. Bazan GC. Tretiak S. Mukamel S. J. Am. Chem. Soc.  2000,  122:  1289 
    CrossrefGoogle Scholar
  • 22 Beletskaya IP. Cheprakov AV. Chem. Rev.  2000,  100:  3009 
    Google Scholar
  • 23 Renak M. Bartholomew GP. Wang S. Ricatto PJ. Lachicotte RJ. Bazan GC. J. Am. Chem. Soc.  1999,  121:  7787 
    CrossrefGoogle Scholar
  • 24 Heck RF. Org. React.  1982,  27:  345 
    Google Scholar
  • 25 Wadsworth WS. Org. React.  1977,  25:  73 
    Google Scholar
  • 26 Jin J.-I. Park C.-K. Shim H.-K. Polymer  1994,  35:  480 
    CrossrefGoogle Scholar
  • 27 van der Made AW. van der Made RH. J. Org. Chem.  1993,  58:  1262 
    Google Scholar
  • 28 Khurana JM. Maikap GC. J. Indian Chem. Soc.  1999,  76:  216 
    Google Scholar
  • 29 Reich HJ. Cram DJ. J. Am. Chem. Soc.  1969,  91:  3534 
    CrossrefGoogle Scholar
  • 30 Zyss J. Ledoux I. Volkov S. Chernyak V. Mukamel S. Bartholomew GP. Bazan GC. J. Am. Chem. Soc.  2000,  122:  11956 
    CrossrefGoogle Scholar
  • 31 Klessinger M. Michl J. Excited States and Photochemistry of Organic Molecules   VCH Publishers; New York: 1995. 
    Google Scholar
11

‘Morphology’ in crystallography refers to the shape of the crystal with implications to the arrangement of subunits on the molecular scale. In organic electronics this term is extended to encompass intermolecular arrangements within non-crystalline or amorphous environments.

32

Zyss, J.; Ledoux, I.; Bartholomew, G. P.; Bazan, G. C.; Mukamel, S.; Volkov, S. work in progress.

33

Rumi, M.; Bartholomew, G. P.; Perry, J.; Bazan, G. C. work in progress.