Three-dimensional electronic delocalization in chiral conjugated polymers

Angewandte Chemie - International Edition

Volumn 41, Issue 22, 2002, Pages 4225-4230

  Zahn, Steffen ^a   Swager, Timothy M ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Circular dichroism; Fluorescence spectroscopy; Materials science; Polymers; Supramolecular chemistry

Indexed keywords

STEREOCHEMISTRY; TOLUENE;

ELECTRONIC DELOCALIZATION;

POLYMERS;

POLY(PHENYLENE ETHYNYLENE); POLYMER; SOLVENT; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL ANALYSIS; CHIRALITY; COMBINATORIAL CHEMISTRY; CONJUGATION; DIAGNOSTIC APPROACH ROUTE; ELECTRONICS; MOLECULAR STABILITY; POLYMERIZATION; PUBLICATION; QUANTUM CHEMISTRY; QUANTUM MECHANICS; SOLVENT EFFECT; STRUCTURE ANALYSIS; THREE DIMENSIONAL IMAGING;

EID: 85047695700     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Article

References (29)

1. A. Rose, C. G. Lugmair, T. M. Swager, J. Am. Chem. Soc. 2001, 123, 11298.
2. H. Sirringhaus, P. J. Brown, R. H. Friend, M. M. Nielsen, K. Bechgaard, B. M. W. Langeveld-Voss, A. J. H. Spiering, R. A. J. Janssen, E. W. Meijer, P. Herwig, D. M. De Leeuw, Nature 1999, 401, 685.
3. R. H. Friend, R. W. Gymer, A. B. Holmes, J. H. Burroughes, R. N. Marks, C. Taliani, D. D. C. Bradley, D. A. dos Santos, J.-L. Brédas, M. Logdlund, W. R. Salaneck, Nature 1999, 397, 121; S. Sibley, M. E. Thompson, P. E. Burrows, S. R. Forrest. Optoelectron. Prop. Inorg. Compd. 1999, 29.
4. R. H. Friend, R. W. Gymer, A. B. Holmes, J. H. Burroughes, R. N. Marks, C. Taliani, D. D. C. Bradley, D. A. dos Santos, J.-L. Brédas, M. Logdlund, W. R. Salaneck, Nature 1999, 397, 121; S. Sibley, M. E. Thompson, P. E. Burrows, S. R. Forrest. Optoelectron. Prop. Inorg. Compd. 1999, 29.
5. D. T. McQuade, A. E. Pullen, T. M. Swager, Chem. Rev. 2000, 100, 2537.
6. C. J. Brabec, N. S. Sariciftci, J. C. Hummelen, Adv. Funct. Mater. 2001, 11, 15.
7. T. Sato, D.-L. Jiang, T. Aida, J. Am. Chem. Soc. 1999, 121, 10658.
8. J.-S. Yang, T. M. Swager, J. Am. Chem. Soc. 1998, 120, 5321.
9. D. T. McQuade, J. Kim, T. M. Swager, J. Am. Chem. Soc. 2000, 122, 5885.
10. J.-L. Brédas, J. Cornil, D. Beljonne, D. A. dos Santos, Z. Shuai, Acc. Chem. Res. 1999, 32, 267.
11. R. Deans, J. Kim, M. Machacek, T. M. Swager, J. Am. Chem. Soc. 2000, 122, 8565.
12. This model is most properly used to understand only very weakly interacting chromophores. However, it guided our studies. M. Kasha in Spectroscopy of the Excited State (Ed.: B. Di Bartollo), Plenum, New York, 1976, pp. 337-363.
13. J. Kim, T. M. Swager, Nature 2001, 411, 1030.
14. R. Fiesel, U. Scherf, Macromol. Rapid Commun. 1998, 19, 427.
15. -1) is reported, which is considerably (34 nm) blue-shifted relative to the carefully characterized polymers investigated here, and to other achiral polymers having the same electronic structure. Hence we attribute the differences to the analysis in the previous studies of very low molecular-weight oligomeric samples.
16. B. M. W. Langeveld-Voss, R. A. Janssen, M. P. T. Christiaans, S. C. J. Meskers, H. P. J. M. Dekkers, E. W. Meijer, J. Am. Chem. Soc. 1996, 118, 4908.
17. A. F. M. Kilbinger, A. P. H. J. Schenning, F. Goldoni, W. J. Feast, E. W. Meijer, J. Am. Chem. Soc. 2000, 122, 1820.
18. B. M. W. Langeveld-Voss, D. Beljonne, Z. Shuai, R. A. J. Janssen, S. C. J. Meskers, E. W. Meijer, J.-L. Brédas, Adv. Mater. 1998, 10, 1343; B. M. W. Langeveld-Voss, R. A. J. Janssen, E. W. Meijer, J. Mol. Struct. 2000, 521, 285.
19. B. M. W. Langeveld-Voss, D. Beljonne, Z. Shuai, R. A. J. Janssen, S. C. J. Meskers, E. W. Meijer, J.-L. Brédas, Adv. Mater. 1998, 10, 1343; B. M. W. Langeveld-Voss, R. A. J. Janssen, E. W. Meijer, J. Mol. Struct. 2000, 521, 285.
20. N. Berova, K. Nakanishi in Circular Dichroism: Principles and Applications (Eds.: N. Berova, K. Nakanishi, R. W. Woody), Wiley-VCH, New York, 2000, pp. 337-382.
21. We found that thin films of these materials do not aggregate even with extended thermal annealing at 160°C. Possibly the PPE main chains are collinear and kept apart by the presence of the pentiptycene groups.
22. -6 mmHg or about 10 ppb. Handbook of Physical Properties of Organic Chemicals (Eds.: P. H. Howard, W. M. Meylan), CRC, Boca Raton, FL, 1997.
23. For comparison, other electronic polymers reportedly decreased their fluorescence intensity by 8.2 % after exposure to similar vapor concentrations with turbulent flow for 10 min (H. Sohn, R. M. Calhoun, M. J. Sailor, W. C. Trogler, Angew. Chem. Int. Ed. 2001, 113, 2162; Angew. Chem. Int. Ed. 2001, 40, 2104). Hence 3, which was studied under static conditions, is at least 560 times more sensitive.
24. For comparison, other electronic polymers reportedly decreased their fluorescence intensity by 8.2 % after exposure to similar vapor concentrations with turbulent flow for 10 min (H. Sohn, R. M. Calhoun, M. J. Sailor, W. C. Trogler, Angew. Chem. Int. Ed. 2001, 113, 2162; Angew. Chem. Int. Ed. 2001, 40, 2104). Hence 3, which was studied under static conditions, is at least 560 times more sensitive.
25. Y. Liu, R. C. Mills, J. M. Boncella, K. S. Schanze, Langmuir 2001, 17, 7452; G. A. Bakken, G. W. Kauffman, P. C. Jurs, K. J. Albert, S. S. Stitzel, Sens. Actuators B 2001, 79, 1.
26. Y. Liu, R. C. Mills, J. M. Boncella, K. S. Schanze, Langmuir 2001, 17, 7452; G. A. Bakken, G. W. Kauffman, P. C. Jurs, K. J. Albert, S. S. Stitzel, Sens. Actuators B 2001, 79, 1.
27. Y.-S. Yang, T. M. Swager, J. Am. Chem. Soc. 1998, 120, 11864.
28. The CD and absorption spectra end at 50:50 chloroform:methanol as the rigid, gridlike aggregates precipitate readily at higher methanol content. The fluorescence spectra could be recorded up to 30:70 chloroform:methanol as the concentration of the polymer was only 1/ 10 of that of the absorption studies and therefore precipitation occurred at higher methanol concentrations.
29. Similarly, 3 had a photoluminescence efficiency which was four times higher than that of 2 in films of identical optical density.