[en] Regulating the twist: Tunable supramolecular chirality is induced in an achiral helical self-assembly (P, M; see picture) by hydrogen-bonded chiral guest molecules (yellow and purple rods). Chiroptical probing of the p-conjugated chromophore reveals the mechanistic pathways of chiral induction. 'Majority rules' and 'sergeant and soldiers' experiments give insight into the chiral amplification in the stacks.
Disciplines :
Chemistry
Author, co-author :
George, S.J.
Tomovic, Z.
Smulders, M.M.J.
de Greef, T.F.A.
Leclère, Philippe ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux
Meijer, E.W.
Schenning, A.P.H.J.
Language :
English
Title :
Helicity Induction and Amplification in an Oligo(p-phenylenevinylene) Assembly through Hydrogen-Bonded Chiral Acids
Publication date :
05 November 2007
Journal title :
Angewandte Chemie
ISSN :
0044-8249
Publisher :
John Wiley & Sons, United Kingdom
Volume :
46
Issue :
43
Pages :
8206-8211
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S817 - Chimie des matériaux nouveaux
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
Commentary :
Publié le 20 septembre 2007
Lecture en ligne: http://onlinelibrary.wiley.com/doi/10.1002/anie.200702730/pdf
a) Y. Okamoto, T. Nakano, Chem. Rev. 1994, 94, 349;
b) E. Yashima, K. Maeda, T. Nishimura, Chem. Eur. J. 2004, 10, 42;
c) J. Aimi, K. Oya, A. Tsuda, T. Aida, Angew. Chem. 2007, 119, 2070;
Angew. Chem. Int. Ed. 2007, 46, 2031;
d) M. Kauranen, T. Verbiest, C. Boutton, M. N. Teerenstra, K. Clays, A. J. Schouten, R. J. M. Nolte, A. Persoons, Science 1995, 270, 966;
e) T. Verbiest, S. Van Elshocht, M. Kauranen, L. Hellemans, I. Snauwaert, C. Nuckolls, T. J. Katz, A. Persoons, Science 1998, 282, 913.
For reviews on chiral amplification in macromolecular systems, see a) M. M. Green, J.-W. Park, T. Sato, A. Teramoto, S. Lifson, R. L. B. Selinger, J. V. Selinger, Angew. Chem. 1999, 111, 3328;
Angew. Chem. Int. Ed. 1999, 38, 3138;
b) M. M. Green, K.-S. Cheon, S.-Y. Yang, J.-W. Park, S. Swansburg, W. Liu, Acc. Chem. Res. 2001, 34, 672.
For recent reviews on chiral amplification in supramolecular assemblies, see a) A. E. Rowan, R. J. M. Nolte, Angew. Chem. 1998, 110, 65;
Angew. Chem. Int. Ed. 1998, 37, 63 ;
b) C. Schmuck, Angew. Chem. 2003, 115, 2552;
Angew. Chem. Int. Ed. 2003, 42, 2448;
c) L. Brunsveld, E. W. Meijer, A. E. Rowan, R. J. M. Nolte, Top. Stereochem. 2003, 24, 373;
d) M. A. Mateos-Timoneda, M. Crego-Calama, D. N. Reinhoudt, Chem. Soc. Rev. 2004, 33, 363;
e) K. Maeda, E. Yashima, Top. Curr. Chem. 2006, 265, 47.
P. Cintas, Angew. Chem. 2007, 119, 4090;
Angew. Chem. Int. Ed. 2007, 46, 4016.
For helical systems with chiral monomers, see a) A. R. A. Palmans, J. A. J. M. Vekemans, E. E. Havinga, E. W. Meijer, Angew. Chem. 1997, 109, 2763;
Angew. Chem. Int. Ed. Engl. 1997, 36, 2648;
b) H. Engelkamp, S. Middelbeek, R. J. M. Nolte, Science 1999, 284, 785;
c) J. H. Hirschberg, L. Brunsveld, A. Ramzi, J. A. J. M. Vekemans, R. P. Sijbesma, E. W. Meijer, Nature 2000, 407, 167;
d) R. B. Prince, L. Brunsveld, E. W. Meijer, J. S. Moore, Angew. Chem. 2000, 112, 234;
Angew. Chem. Int. Ed. 2000, 39, 228;
e) J. J. van Gorp, J. A. J. M. Vekemans, E. W. Meijer, J. Am. Chem. Soc. 2002, 124, 14759;
f) M. L. Bushey, A. Hwang, P. W. Stephens, C. Nuckolls, Angew. Chem. 2002, 114, 2952;
Angew. Chem. Int. Ed. 2002, 41, 2828;
g) S. J. George, A. Ajayaghosh, P. Jonkheijm, A. P. H. J. Schenning, E. W. Meijer, Angew. Chem. 2004, 116, 3504;
Angew. Chem. Int. Ed. 2004, 43, 3422;
h) J. J. D. de Jong, L. N. Lucas, R. M. Kellog, J. H. van Esch, B. L. Feringa, Science 2004, 304, 278;
i) A. Lohr, M. Lysetska, F. Würthner, Angew. Chem. 2005, 117, 5199;
Angew. Chem. Int. Ed. 2005, 44, 5071;
j) B. W. Messmore, P. A. Sukerkar, A. I. Stupp, J. Am. Chem. Soc. 2005, 127, 7992;
k) T. Ishi-i, R. Kuwahara, A. Takata, Y. Jeong, K. Sakurai, S. Mataka, Chem. Eur. J. 2006, 12, 763;
l) A. Ajayaghosh, R. Varghese, S. J. George, C. Vijayakumar, Angew. Chem. 2006, 118, 1159;
Angew. Chem. Int. Ed. 2006, 45, 1141.
a) H. Fenniri, B.-L. Deng, A. E. Ribbe, J. Am. Chem. Soc. 2002, 124, 11064;
b) T. Ishi-i, M. Crego-Calama, P. Timmerman, D. N. Reinhoudt, S. Shinkai, Angew. Chem. 2002, 114, 2004;
Angew. Chem. Int. Ed. 2002, 41, 1924.
F. H. Beijer, R. P. Sijbesma, H. Kooijman, A. L. Spek, E. W. Meijer, Angew. Chem. 1998, 110, 79;
Angew. Chem. Int. Ed. 1998, 37, 75.
a) A. P. H. J. Schenning, P. Jonkheijm, E. Peeters, E. W. Meijer, J. Am. Chem. Soc. 2001, 123, 409;
b) P. Jonkheijm, F. J. M. Hoeben, R. Kleppinger, J. van Herrikhuyzen, A. P. H. J. Schenning, E. W. Meijer, J. Am. Chem. Soc. 2003, 125, 15941.
See Supporting Information for details.
Based on the association constant (2 × 10 4M-1) of the chiral analogues in chloroform, we propose that A-OPVUT, in toluene at 1 mM concentration and at room temperature, exists as hydrogen-bonded dimers.
We assume the dimerization constant of R-CA in toluene is approximately kd = 446 M-1; see: Y. Fujii, H. Yamada, M. Mizuta, J. Phys. Chem. 1988, 92, 6768. A-OPVUT exists fully as dimers (kd = 2 × 104 M-1) with two independent binding sites. See Supporting Information for details.
P. Jonkheijm, P. van der Schoot, A. P. H. J. Schenning, E. W. Meijer, Science 2006, 313, 80.
Critical gelator concentrations of A-OPVUT in MCH and toluene were determined to be 1 mM and 2 mM, respectively.
Best fits (based on residual analysis) were obtained by assuming the dimerization constant of acid is zero, which is based on the preparation method of the complexes. R-CA is already hydrogen-bonded to the OPV dimers at high temperatures, and upon cooling, the CD signal appears owing to the stacking of this supramolecular complex. See Supporting Information for details.
S or R-citronellol can also induce a preference for homochiral stacks. However more than 500 equivalents of chiral alcohol is required for the saturation of chirality, suggesting that the interaction between alcohol and OPV is less strong compared to the chiral acid guest (See Supporting Information). No chiral induction occurs when R-2,6-dimethyl octane is added.
Surprisingly, we have observed a remarkable linear-dichroism effect in dodecane upon cooling the sample slowly for similar achiral OPV derivatives even in dilute solution, as a result of convective flow and resultant alignment of fibers in the cuvette (10-5 M). M. Wolffs, S. J. George, Ž. Tomović, S. C. J. Meskers, A. P. H. J. Schenning, E. W. Meijer, Angew. Chem. 2007, 119, 8351-8353;
Angew. Chem. Int. Ed. 2007, 46, 8203-8205.
We have used the CD values at higher temperatures (313 K) for the titration and Job plot graphs, to avoid any significant contribution from the LD.
E. Yashima, K. Maeda, Y. Okamoto, Nature 1999, 399, 449.
M. M. Green, B. A. Garetz, B. Munoz, H. Chang, S. Hoke, R. G. Cooks, J. Am. Chem. Soc. 1995, 117, 4181.
a) J. van Gestel, A. R. A. Palmans, B. Titulaer, J. A. J. M. Vekemans, E. W. Meijer, J. Am. Chem. Soc. 2005, 127, 5490;
b) W. Jin, T. Fukushima, M. Niki, A. Kosaka, N. Ishii, T. Aida, Proc. Natl. Acad. Sci. USA 2005, 102, 10801.
