A redox-controlled molecular switch based on the reversible C-C bond formation in octamethoxytetraphenylene

Angewandte Chemie - International Edition

Volumn 39, Issue 4, 2000, Pages 809-812

  Rathore, Rajendra ^a   Magueres, Pierre Le ^a   Lindeman, Sergey V ^a   Kochi, Jay K ^a  

^a University of Houston ^*  (United States)

Author keywords

Cyclic voltammetry; Electrochemistry; Molecular devices; Radicals

Indexed keywords

BENZENE DERIVATIVE; CARBON;

ARTICLE; CHEMICAL STRUCTURE; COLOR; ELECTRON TRANSPORT; OXIDATION REDUCTION REACTION; STOICHIOMETRY; X RAY CRYSTALLOGRAPHY;

EID: 0034681497     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(20000218)39:4<809::AID-ANIE809>3.0.CO;2-6     Document Type: Article

References (44)

1. a) L. Fabbrizzi, A. Poggi, Chem. Soc. Rev. 1995, 198;
2. b) B. L. Feringa, W. F. Jager, B. de Lange, Tetrahedron 1993, 49, 8267, and references therein;
3. c) R. Rathore, S. V. Lindeman, J. K. Kochi, Angew. Chem. 1998, 110, 1665;
4. Angew. Chem. Int. Ed. 1998, 37, 1585.
5. a) W. B. Davis, W. A. Svec, M. A. Ratner, M. R. Wasielewski, Nature 1998, 596, 60;
6. b) J.-M. Tour, J. Schumm, D. L. Pearson, Macromolecules 1994, 27, 2348;
7. c) D. K. Das-Gupta in Introduction to Molecular Electronics (Eds.: M. C. Petty, M. R. Bryce, D. Bloor), Edward Arnold, London, 1995, pp. 47-71;
8. d) R. E. Martin, F. Diederich, Angew. Chem. 1999, 111, 1440;
9. Angew. Chem. Int. Ed. 1999, 38, 1350;
10. e) D. A. Parthenopoulos, P. M. Rentzepis, Science 1989, 245, 843.
11. a) H. Meier, Angew. Chem. 1992, 104, 1425;
12. Angew. Chem. Int. Ed. Engl. 1992, 31, 1399;
13. b) M. Takeshita, C. F. Soong, M. Irie, Tetrahedron Lett. 1998, 39, 7717;
14. c) D. Philp, J. F. Stoddart, Angew. Chem. 1996, 108, 1242;
15. Angew. Chem. Int. Ed. Engl. 1996, 35, 1154.
16. a) D. J. Cardenas, A. Livoreil, J.-P. Sauvage, J. Am. Chem. Soc. 1996, 118, 11980;
17. b) T. Suzuki, H. Takahashi, J.-I. Nishida, T. Tsuji, Chem. Commun. 1998, 1331;
18. c) T. Suzuki, M. Kondo, T. Nakamura, T. Fukushima, T. Miyashi, J. Chem. Soc. Chem. Commun. 1997, 2325.
19. a) P. R. Ashton, V. Balzani, J. Becher, A. Credi, M. C. T. Fyfe, G. Mattersteig, S. Menzer, M. B. Nielsen, F. M. Raymo, J. F. Stoddart, M. Venturi, D. J. Williams, J. Am. Chem. Soc. 1999, 121, 3951, and references therein;
20. b) R. Deans, A. Niemz, E. C. Breinlinger, V. M. Rotello, J. Am. Chem. Soc. 1997, 119, 10863.
21. The disk-shaped hexamethoxytriphenylene is planar and has been extensively studied owing to its liquid-crystalline properties. However, its higher homologue octamethoxytetraphenylene (OMT) is heretofore unknown.
22. Note that the dark-red solution obtained upon electrooxidation of OMT was EPR-silent. Either an electroreduction or a treatment of the red-colored solution with zinc dust led to the recovery of neutral OMT in quantitative yield.
23. 0 = 1.1-1.3 V vs. SCE) are useful one-electron oxidants, see: R. Rathore, J. K. Kochi, J. Org. Chem. 1994, 60, 4399.
24. E. K. Kim, J. K. Kochi, J. Am. Chem. Soc. 1991, 113, 4962.
25. R. Rathore, A. S. Kumar, S. V. Lindeman, J. K. Kochi, J. Org. Chem. 1998, 63, 5847.
26. - as one-electron oxidant: R. Rathore, P. Le Magueres, J. K. Kochi, unpublished results.
27. The redox stoichiometry in Equation (2) is further confirmed by coulometry at a constant potential of 1.25 V (vs. SCE) in dichloromethane (containing 0.2 M tetra-n-butylammonium hexafluorophosphate as supporting electrolyte) at 0°C.
28. The identity of liberated NO gas is confirmed by UV/Vis and IR spectroscopy, see refs. [8, 9].
29. 0 = 2.15 V vs. SCE) and readily oxidizes a variety of aromatic donors to their radical cations, see: R. Rathore, S. M. Hubig, J. K. Kochi, J. Am. Chem. Soc. 1997, 119, 11 468.
30. Compare: R. Rathore, J. K. Kochi, Acta. Chem. Scand. 1998, 52, 114.
31. Methoxy groups are omitted for the sake of clarity.
32. 2+ around C11 and C31 are: C12-C11-C31 105.2, C12-C11-C42112.6, C16-C11-C12114.7, C16-C11-C42 106.4, C16-C11-C31 116.8, C42-C11-C31 100.5, C32-C31-C11 105.1, C32-C31-C22 106.5, C36-C31-C32 114.1, C36-C31-C11 117.8, C36-C31-C22 110.7, C11-C31-C22 101.3.
33. For the definition of quinoidal distortion, see: R. Rathore, S. V. Lindeman, A. S. Kumar, J. K. Kochi, J. Am. Chem. Soc. 1998, 120, 6931.
34. a) M. Horner, S. Hünig, J. Am. Chem. Soc. 1977, 99, 6122;
35. b) R. Rathore, J. K. Kochi, J. Org. Chem. 1998, 63, 8630.
36. D. K. Gosser, P. H. Rieger, Anal. Chem. 1988, 60, 1159. A Fortran listing or PC version (Turbo-Pascal 5) of the program is available upon request from D. K. Gosser, City College, City University of New York. We thank Professor Gosser for providing us a copy of the PC version of the program.
37. A similar ECE mechanism is applicable to other (oxidative) biaryl syntheses, see: A. Ronlan, O. Hammerich, V. D. Parker, J. Am. Chem. Soc. 1973, 95, 7132.
38. The distonic radical cations have ample literature precedent in the synthesis of a variety of biaryls, see : O. Hammerich, V. D. Parker, Adv. Phys. Org. Chem. 1984, 20, 55, and references therein.
39. -1 based on time-resolved absorption measurements upon diffusional electron-transfer quenching of photoexcited chloranil, see ref. [14]. Thus, the transient spectrum obtained 1 μs after laser excitation (10 ns) of chloranil (8 mM) in the presence of OMT (10 mM) shows an absorption band at 450 nm with a shoulder at 420 nm, characteristic of a chloranil radical anion, as well as a band at 370 nm and a weak (broad) absorption at about 660 nm. The latter two absorptions are tentatively assigned to the spectrum of the distonic radical cation since it lacks the characteristic absorption wavelengths of the radical cations of either the dimethoxybenzenes or the methoxylated biphenyls (see: T. Shida, Electronic Absorption Spectra, Elsevier, New York, 1988).
40. Cyclohexadienyl-type radicals are known to undergo oxidation at circa 0 V (vs. SCE), see: O. Hammerich, V. D. Parker, Adv. Phys. Org. Chem. 1984, 20, 55.
41. See also: R. C. Haddon, S. V. Chichester, S. M. Stein, J. H. Marshall, A. M. Mujsce, J. Org. Chem. 1987, 52, 711.
42. H. Gilman, B. J. Gaj, J. Org. Chem. 1957, 22, 447.
43. M. Iyoda, S. M. Humayun, A. Vorasingha, Y. Kuwatani, M. Yoshida, Tetrahedron Lett. 1998, 39, 5393.
44. G. M. Sheldrick, SHELSX-S6, University of Göttingen (Germany), 1986.