Influence of topology on the long-range electron-transfer phenomenon

Chemistry - A European Journal

Volumn 7, Issue 1, 2001, Pages 240-250

  Rovira, Concepció ^a   Ruiz Molina, Daniel ^a   Elsner, Olaf ^a   Vidal Gancedo, Jose ^a,b   Bonvoisin, Jacques ^b   Launay, Jean Pierre ^b   Veciana, Jaume ^a  

^a INSTITUT DE CIÈNCIA DE MATERIALS DE BARCELONA ICMAB CSIC   (Spain)

^b CEMES CNRS   (France)

Author keywords

Electron transfer; Mixed valent compounds; Organic radicals; Radical ions

Indexed keywords

ORGANIC COMPOUND; RADICAL;

ARTICLE; CHEMICAL REACTION; COVALENT BOND; ELECTROCHEMISTRY; ELECTRON SPIN RESONANCE; ELECTRON TRANSPORT; MOLECULAR INTERACTION; OXIDATION REDUCTION REACTION; REACTION ANALYSIS; SYNTHESIS;

EID: 0035808224     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20010105)7:1<240::AID-CHEM240>3.0.CO;2-H     Document Type: Article

References (60)

1. a) A. Harriman, R. Ziessel, Coord. Chem. Rev. 1998, 171, 331;
2. b) M. N. Paddon-Row, Acc. Chem. Res. 1994, 27, 18;
3. c) M. R. Wasielewski, Chem. Rev. 1992, 92, 435.
4. 5 decrease in required size. In addition, the response times of molecular devices can be in the range of femtoseconds, while the fastest current devices operate in the nanosecond regime: a) J. M. Tour, M. Kozaki, J. M. J. Seminario, J. Am. Chem. Soc. 1998, 120, 8486;
5. b) J. M. Seminario, J. M. Tour in Molecular Electronics-Science and Technology (Eds. : A. Aviram, M. A. Ratner), New York Academy of Science, New York, 1998, p. 69.
6. J.-P. Sauvage, J.-P. Collin, J.-C. Chambron, S. Guillerez, C. Coudret, Chem. Rev. 1994, 94, 993.
7. See for instance: a) R. J. Crutchley, Adv. Inorg. Chem. 1994, 41, 273;
8. b) C. Creutz, Prog. Inorg. Chem. 1983, 30, 1.
9. a) S. F. Nelsen, H. Q. Tran, M. A. Nagy, J. Am. Chem. Soc. 1998, 120, 298;
10. b) S. F. Nelsen, M. R. Ramm, J. J. Wolf, D. R. Powell, J. Am. Chem. Soc. 1997, 119, 6863;
11. c) K. Lahlil, A. Moradpour, C. Bowlas, F. Menou, P. Cassoux, J. Bonvoisin, J. P. Launay, G. Dive, D. Dehareng, J. Am. Chem. Soc. 1995, 117, 9995;
12. d) J. Bonvoisin, J. P. Launay, M. Van der Auweraer, F. C. De Schryver, J. Phys. Chem. 1994, 98, 5052;
13. e) S. F. Rak, L. L. Miller, J. Am. Chem. Soc. 1992, 114, 1388;
14. f) S. Utamapanya, A. Rajca, J. Am. Chem. Soc. 1991, 113, 9242;
15. g) J. P. Telo, C. B. L. Shohoji, B. Herold, G. Grampp, J. Chem. Soc. Faraday Trans. 1992, 88, 47;
16. h) F. Gerson, T. Wellauer, A. M. Oliver, M. N. Paddon-Row, Helv. Chim. Acta 1990, 73, 1586;
17. i) M. Ballester, I. Pascual, J. Riera, J. Castañer, J. Org. Chem. 1991, 56, 217.
18. a) M. Ballester, J. Riera, J. Castañer, A. Rodríguez, Tetrahedron Lett. 1971, 2079;
19. b) M. Ballester, J. Riera, J. Castañer, J. Veciana, C. Rovira, J. Org. Chem. 1982, 47, 4498;
20. c) M. Ballester, Acc. Chem. Res. 1985, 297, 131;
21. d) J. Veciana, J. Riera, J. Castañer, N. Ferrer, J. Organomet. Chem. 1985, 297, 131;
22. e) O. Armet, J. Veciana, C. Rovira, J. Riera, J. Castañer, E. Molins, J. Rius, C. Miravitlles, S. Olivella, J. Brichfeus, J. Phys. Chem. 1987, 91, 5608, and references cited therein.
23. J. Sedo, D. Ruiz, J. Vidal-Gancedo, C. Rovira, J. Bonvoisin, J.-P. Launay, J. Veciana, Adv. Mater. 1996, 8, 748.
24. V. Grosshenny, A. Harriman, R. Ziessel, Angew. Chem. 1995, 107, 1211; Angew. Chem. Int. Ed. Engl. 1995, 34, 1100, and references therein.
25. V. Grosshenny, A. Harriman, R. Ziessel, Angew. Chem. 1995, 107, 1211; Angew. Chem. Int. Ed. Engl. 1995, 34, 1100, and references therein.
26. a) C. Patoux, J.-P. Launay, M. Beley, S. Chodorowski-Kimmes, J.-P. Collin, S. James, J.-P. Sauvage, J. Am. Chem. Soc. 1998, 120,3717;
27. b) F. Barigelletti, L. Flamigni, V. Balzani, J.-P. Collin, J.-P. Sauvage, E. C. Constable, A. M. W. Cargilll Thompson, J. Chem. Soc. Chem. Commun. 1993, 942; F. Barigelletti, L. Flamigni, V. Balzani, J.-P. Collin, J.-P. Sauvage, A. Sour, E. C. Constable, A. M. W. Cargill1 Thompson, J. Am. Chem. Soc. 1994, 116, 7692;
28. b) F. Barigelletti, L. Flamigni, V. Balzani, J.-P. Collin, J.-P. Sauvage, E. C. Constable, A. M. W. Cargilll Thompson, J. Chem. Soc. Chem. Commun. 1993, 942; F. Barigelletti, L. Flamigni, V. Balzani, J.-P. Collin, J.-P. Sauvage, A. Sour, E. C. Constable, A. M. W. Cargill1 Thompson, J. Am. Chem. Soc. 1994, 116, 7692;
29. c) A. C. Benniston, V. Goulle, A. Harriman, J. M. Lehn, B. Marczinke, J. Phys. Chem. 1994, 98, 7798.
30. In order to optimize the intramolecular electron-transfer rates between two terminal radicals, the synthesis of the bridge requires the use of molecular units with highly restricted conformational mobility, high solubility, and high thermal and electrochemical stabilities: "Atomic and Molecular Wires", A. Gourdon NATO ASI Ser. E: Applied Sciences, 1997, 198, 89.
31. Preliminary results have already been presented in a communication: J. Bonvoisin, J.-P. Launay, C. Rovira, J. Veciana, Angew. Chem. 1994, 106, 2190; Angew. Chem. Int. Ed. Engl. 1994, 33, 2106.
32. Preliminary results have already been presented in a communication: J. Bonvoisin, J.-P. Launay, C. Rovira, J. Veciana, Angew. Chem. 1994, 106, 2190; Angew. Chem. Int. Ed. Engl. 1994, 33, 2106.
33. R. Ziessel, M. Hissler, A. El-Ghayoury, A. Harriman, Coord. Chem. Rev. 1998, 178-180, 1251.
34. M. Ballester, J. Veciana, J. Riera, J. Castañer, C. Rovira, O. Armet, J. Org. Chem. 1986, 51, 2472.
35. For other strongly (E)-selective reactions, see for example: H. Pommer, A. Nurenbach, Angew. Chem. 1977, 89, 437; Angew. Chem. Int. Ed. Engl. 1977, 16, 423.
36. For other strongly (E)-selective reactions, see for example: H. Pommer, A. Nurenbach, Angew. Chem. 1977, 89, 437; Angew. Chem. Int. Ed. Engl. 1977, 16, 423.
37. H. O. House, Modern Synthetic Reactions, 2nd ed., Benjamin, Menlo Park, 1972, p. 608.
38. a) K. Wurst, O. Elsner, H. Schottenberger, Synlett 1995, 833;
39. b) J.-G. Rodríguez, A. Õnate, R. M. Martin-Villamil, I. Fonseca, J. Organomet. Chem. 1996, 513, 71.
40. L. Fitjer, U. Quabeck, Synth. Commun. 1985, 15, 855.
41. For a review see: J. Stec, Acc. Chem. Res. 1983, 16, 411.
42. 2 axes), the molecule always has at least two enantiomeric forms owing to the intrinsic stereogenic center (helicity) of any propeller that gives chirality to the molecule. If the helix adopts a clockwise sense the enantiomer is called Plus (P), whereas if it adopts the opposite sense is called Minus (M). For diradicals 1 and 2 it is easy to predict the existence of three stereoisomers: one pair of enantiomers - namely (P,P) and (M,M) -and a meso form - namely (M*,P*) - due to the presence of two triphenylmethyl stereogenic centers. (N. Ventosa, D. Ruiz-Molina, J. Sedó, C. Rovira, X. Tomas, J.-J. André, A. Bieber, J. Veciana, Chem. Eur. J. 1999, 5, 3533). Semiempirical calculations were done by using initial input molecules that had one of the triphenylmethyl units in the M form and the other in the P form. It was also checked that the use of another stereoisomer did not have any influence on the final minimized geometries.
43. 2 axes), the molecule always has at least two enantiomeric forms owing to the intrinsic stereogenic center (helicity) of any propeller that gives chirality to the molecule. If the helix adopts a clockwise sense the enantiomer is called Plus (P), whereas if it adopts the opposite sense is called Minus (M). For diradicals 1 and 2 it is easy to predict the existence of three stereoisomers: one pair of enantiomers - namely (P,P) and (M,M) - and a meso form - namely (M*,P*) - due to the presence of two triphenylmethyl stereogenic centers. (N. Ventosa, D. Ruiz-Molina, J. Sedó, C. Rovira, X. Tomas, J.-J. André, A. Bieber, J. Veciana, Chem. Eur. J. 1999, 5, 3533). Semiempirical calculations were done by using initial input molecules that had one of the triphenylmethyl units in the M form and the other in the P form. It was also checked that the use of another stereoisomer did not have any influence on the final minimized geometries.
44. It is well known that the unpaired electron of highly chlorinated triphenylmethyl radicals and the negative charge of the corresponding carbanions are mainly localized on the alpha carbons (see ref. [6], and references cited therein). Therefore, the two alpha carbon atoms of 1 and 2 can be considered, in a first approximation, as the electron active sites for the electron-transfer phenomena. It should also be considered that the distance between the electron active sites may change from one conformer to the other. For instance, the through-space distance between the electron active sites for diradical 2 ranges from 16.9 to 15.1 Å along the different conformational isomers obtained simply by rotating the single bond that connects the central phenylene unit and one of the vinylene moieties.
45. A. Hradsky, B. Bildstein, N. Schuler, H. Schottenberger, P. Jaitner, K.-H. Ongania, K. Wurst, J.-P. Launay, Organometallics 1997, 16, 392.
46. No differences in the magnetic behavior of (E)-3 and (Z)-3 were noticed.
47. S. D. McGlynn, T. Azumi, M. Kinoshita in Molecular Spectroscopy of the Triplet State, PrenticeHall, New Jersey, 1969.
48. A.-C. Ribou, J.-P. Launay, K. Takahashi, T. Nihira, S. Tarutani, C. W. Spangler, Inorg. Chem. 1994, 33, 1325.
49. S. F. Nelsen, S. C. Blacstock, Y. Kim, J. Am. Chem. Soc. 1987,109, 677.
50. MOPAC 93.00, a) J. J. Stewart, M. J. S. Dewar, E. G. Zoebish, E. F. Healy, J. Am. Chem. Soc. 1985, 107, 3902;
51. b) M. J. S. Dewar, E. G. Zoebish, J. Mol. Struct.(Theochem) 1988, 180, 1.
52. - was performed by assuming Gaussian profiles in order to separate the intervalence band from other nearby bands (see Figure 4). This deconvolution procedure has already been described in ref. [24] and has the advantage of giving a better estimate of the Marcus λ value.
53. J. Heinzer, J. Mol. Phys. 1971, 22, 167; Quantum Chemistry Program Exchange 1972, No 209.
54. J. Heinzer, J. Mol. Phys. 1971, 22, 167; Quantum Chemistry Program Exchange 1972, No 209.
55. S. F. Nelsen, R. F. Ismagilov, D. A. Trieber II, Science 1997, 278, 846.
56. O. Elsner, D. Ruiz-Molina, J. Vidal-Gancedo, C. Rovira, J. Veciana, Chem. Commun. 1999, 579.
57. C. Patoux, C. Coudret, J. P. Launay, C. Joachim, A. Gourdon, Inorg. Chem. 1997, 36, 5037.
58. a) M. J. Shephard, M. N. Paddon-Row, K. D. Jordan, J. Am. Chem. Soc. 1994, 116, 5328;
59. b) M. N. Paddon-Row, Acc. Chem. Res. 1994, 27, 18, and references cited therein.
60. M. J. S. Dewar, E. G. Zoebisch, E. F. Healy, J. J. P. Stewart, J. Am. Chem. Soc. 1985, 107, 3902.