Terthiophene radical cations end-capped by bicyclo[2.2.2]octene units: Formation of bent π-dimers mutually attracted at the central position

Journal of the American Chemical Society

Volumn 128, Issue 45, 2006, Pages 14470-14471

  Yamazaki, Daisuke ^a   Nishinaga, Tohru ^b   Tanino, Nobuhide ^a   Komatsu, Koichi ^a  

^a KYOTO UNIVERSITY   (Japan)

^b TOKYO METROPOLITAN UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

2 STANNYLTHIOPHENE; 2,5 DIBROMOTHIOPHENE; BICYCLO COMPOUND; BICYCLO[2.2.2]OCTENE; CATION; DIMER; RADICAL; TERTHIOPHENE; THIOPHENE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL STRUCTURE; COLOR; CRYSTAL STRUCTURE; DENSITY FUNCTIONAL THEORY; DIMERIZATION; ELECTRON; OXIDATION; REACTION ANALYSIS; STRUCTURE ANALYSIS; SYNTHESIS; ULTRAVIOLET SPECTROSCOPY; X RAY CRYSTALLOGRAPHY;

EID: 33750985368     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja065995l     Document Type: Article

References (22)

1. For example, see (a) Handbook of Organic Conductive Molecules and Polymers; Nalwa, H. S., Ed.; Wiley: New York, 1997; Vols. 1-4.
2. (b) Handbook of Conducting Polymers, 2nd ed.; Skotheim, T. A., Reynolds, J. R., Elsenbaumer, R. L., Eds.; Marcel Dekker: New York, 1997.
3. (a) Hill, M. G.; Mann, K. R.; Miller, L. L.; Penneau, J.-F. J. Am. Chem. Soc. 1992, 114, 2728-2730.
4. (b) Bauerle, P.; Segelbacher, U.; Gaudl, K.-L.; Huttenlocher, D.; Mehring, M. Angew. Chem., Int. Ed. Engl. 1993, 32, 76-78.
5. (c) Yu, Y.; Gunic, E.; Zinger, B.; Miller, L. L. J. Am. Chem. Soc. 1996, 118, 1013-1018.
6. (d) Brocks, G. J. Chem. Phys. 2000, 112, 5353-5363.
7. (e) Pickholz, M.; dos Santos, M. C. J. Mol. Struct.: THEOCHEM 2005, 717, 99-106.
8. (a) Graf, D. D.; Campbell, J. P.; Mann, K. R.; Miller, L. L. J. Am. Chem. Soc. 1996, 118, 5480-5481.
9. (b) Graf, D. D.; Duan, R. G.; Campbell, J. P.; Miller, L. L.; Mann, K. R. J. Am. Chem. Soc. 1997, 119, 5888-5899.
10. Nishinaga, T.; Komatsu, K. Org. Biomol. Chem. Perspect. 2005, 3, 561-569.
11. For the case of bipyrrole radical cation, see Merz, A.; Kronberger, J.; Dunsch, L.; Neudeck, A.; Petr, A.; Parkanyi, L. Angew. Chem., Int. Ed. 1999, 38, 1442-1446.
12. For reviews, see (a) Komatsu, K.; Nishinaga, T. Synlett Acc. 2005, 187-202.
13. (b) Komatsu, K. Pure Appl. Chem. 2006, 78, 685-697.
14. Nishinaga, T.; Wakamiya, A.; Yamazaki, D.; Komatsu, K. J. Am. Chem. Soc. 2004, 126, 3163-3174.
15. Wakamiya, A.; Yamazaki, D.; Nishinaga, T.; Kitagawa, T.; Komatsu, K. J. Org. Chem. 2003, 68, 8305-8314.
16. The possible steric repulsion between bridgehead hydrogen atoms of the central BCO unit and sulfur atoms in 1 should be unfavorable for the planarization.
17. Calculated according to the method reported by Bäuerle et al. (ref 2b).
18. Thermodynamic parameters for π-dimer formation roughly calculated based on the ESR data are ΔH ≈ -6 kcal/mol and ΔS ≈ -18 eu.
19. 2 carbon atoms at the connecting positions. However, the averaged bond angles at the most pyramidalized carbon is 119.80°, which does not consume much energy. We thank one of the referees for directing our attention to this point.
20. Several trials for estimation of the singlet-triplet energy gap using the ESR data at a temperature range of 180-400 K afforded the most possible value to be in the range of 5-7 kcal/mol.
21. .- in particular), see, for example, (a) Del Sesto, R. E.; Miller, J. S.; Lafuente, P.; Novoa, J. J. Chem. Eur. J. 2002, 8, 4894-4908.
22. (b) Lu, J.-M.; Rosokha, S. V.; Kochi, J. K. J. Am. Chem. Soc. 2003, 125, 12161-12171.