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Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature. Reporter: Zhengming Tang 唐铮铭 Supervisor ： Prof. Jian Pei 2006.11.3. Outline. Introduction Lessons from nature Scientists’ efforts Conclusion and outlook Acknowledgement. Outline. Introduction

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Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

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  1. Self-Assembly In Supramolecular Chemistry-- Inspiration From Nature Reporter: Zhengming Tang 唐铮铭 Supervisor：Prof. Jian Pei 2006.11.3

  2. Outline • Introduction • Lessons from nature • Scientists’ efforts • Conclusion and outlook • Acknowledgement

  3. Outline • Introduction • Lessons from nature • Scientists’ efforts • Conclusion and outlook • Acknowledgement

  4. Introduction Nobel Prize in 1987: Pederson C , Cram D J, Lehn J M. Supramolecular chemistry, a term introduced by Jean-Marie Lehn, is “chemistry beyond the molecule”, that is the chemistry of molecular assemblies using noncovalent bonds. Jean-Marie Lehn, Science 2002, 295, 2400 Freek J. M. Hoeben, E. W. Meijer, Chemical Reviews 2005, 105, 1491

  5. Introduction Freek J. M. Hoeben, E. W. Meijer, Chemical Reviews 2005, 105, 1491

  6. Outline • Introduction • Lessons from nature • Scientists’ efforts • Conclusion and outlook • Acknowledgement

  7. Lessons from nature “The chemist finds illustration, inspiration, and stimulation in natural processes, as well as confidence and reassurance since they are proof that such highly complex systems can indeed be achieved on the basis of molecular components.” Jean-Marie Lehn, 1995 Nature has evolved functional assemblies over millions of years; hence, scientists often gather inspiration from the beautiful structures that are encountered. E. W. Meijer, 2005

  8. Lessons from nature--AQP1selective water permeation Hydrophobic effects Kazuyoshi Murata, Kaoru Mitsuoka, Teruhisa Hirai, Nature 2000, 407, 599-605.

  9. Lessons from nature--light-harvesting protein PE545 Protein PE545 assembled with eight light-absorbing molecules plays a key role in this photosynthetic system Centre for Quantum Information and Quantum Control, University of Toronto, Nature Materials2006, 5, 683-696.

  10. Lessons from nature--light-harvesting protein PE545 Centre for Quantum Information and Quantum Control, University of Toronto, Nature Materials2006, 5, 683-696.

  11. Lessons from nature--DNA bound by base pairs

  12. Outline • Introduction • Lessons from nature • Scientists’ efforts Assembled byhydrogen bond Assembled byп-п interaction Assembled bymetal-ligand Scientists’ bionic results • Conclusion and outlook • Acknowledgement

  13. Outline • Introduction • Lessons from nature • Scientists’ efforts Assembled byhydrogen bond Assembled byп-п interaction Assembled bymetal-ligand Scientists’ bionic results • Conclusion and outlook • Acknowledgement

  14. Scientists’ effortsAssembled by hydrogen bond First noted in 1892 by Nernst Werner proposed his concept of “Nebenvalenz” (minor valence) in 1902 The theory that the hydrogen atom was the center of this weak interaction were first made in 1920 by Huggins as well as Latimer and Rodebush. Bernal and Huggins proposed the actual term “hydrogen bond” in 1935 “The discovery of the Hydrogen Bond could have won someone the Nobel Prize, but it didn’t.” George A. Jeffrey, Wolfram Saenger, 1991

  15. The essence of hydrogen bond • Electrostatic or coulomb energy (ΔECOU) • 2) Exchange repulsion (ΔEEX) • 3) Polarization energy (ΔEPOL) • 4) Charge-transfer energy or covalent bonding (ΔECHT) • 5) Dispersion forces (ΔEDIS). Leonard J. Prins, Peter Timmerman, Angew. Chem. Int. Ed., 2001, 40, 2382-2426

  16. The essence of hydrogen bond Felix H. Beijer, E. W. Meijer, J. Am. Chem. Soc. 1998, 120, 6761-6769

  17. Assembled by hydrogen bond Takashi Kato, Norihiro Mizoshita, Angew. Chem. Int. Ed. , 2006, 45, 38– 68.

  18. Assembled by hydrogen bond Takashi Kato, Norihiro Mizoshita, Angew. Chem. Int. Ed. , 2006, 45, 38– 68.

  19. Assembled by hydrogen bond Design strategy T. Yamaguchi, Takuzo Aida, J. Am. Chem. Soc. 2003, 125, 13934-13935

  20. Assembled by hydrogen bond TEM micrographs of (a,b) 1acid with C60 (c,d) 1acid alone. T. Yamaguchi, Takuzo Aida, J. Am. Chem. Soc. 2003, 125, 13934-13935

  21. Assembled by hydrogen bond Left: Titration of 1acid (1.2 μM) with C70 ([C70]:[1acid] = 0:1–5:1) Right: Titration of 1ester (1.2 μM) with C70 ([C70]:[1ester] = 0:1–6:1) T. Yamaguchi, Takuzo Aida, J. Am. Chem. Soc. 2003, 125, 13934-13935

  22. Assembled by hydrogen bond Supramolecular peapods T. Yamaguchi, Takuzo Aida, J. Am. Chem. Soc. 2003, 125, 13934-13935

  23. Outline • Introduction • Lessons from nature • Scientists’ efforts Assembled byhydrogen bond Assembled byп-п interaction Assembled bymetal-ligand Scientists’ bionic results • Conclusion and outlook • Acknowledgement

  24. Assembled by п-пinteraction Some simple models: M. O. Sinnokrot, C. David Sherrill, J. Am. Chem. Soc. 2004, 126, 7690-7697

  25. Assembled by п-пinteraction TEM photograph of an aggregate of G3-T17-G3. n=5--6 Joke J. Apperloo, Rene A. J. Janssen, J. Am. Chem. Soc., 2001, 123, 6916-6924 Rene A. J. Janssen, Jean M. J. Frechet, Macromolecules, 2000, 33, 7038-7043

  26. Assembled by п-пinteraction Absorption and emission spectra of (a) molecularly dissolved (PL excited at 2.64 eV, solid lines) and aggregated (PL excited at 2.20 eV, dashed lines) G3-T11-G3 in dichloromethane and (b) molecularly dissolved (PL excited at 2.61 eV, solid lines) and aggregated (PL excited at 2.11 eV, dashed lines) G3-T17-G3 in dichloromethane. Joke J. Apperloo, Rene A. J. Janssen, J. Am. Chem. Soc., 2001, 123, 6916-6924 Rene A. J. Janssen, Jean M. J. Frechet, Macromolecules, 2000, 33, 7038-7043

  27. Assembled by п-пinteraction UV-vis (left) and fluorescence (right) spectra of 2 in THF and butanol. Blue shift: Δλ=50 nm for 1; Δλ= 71 nm for 2 Much lower fluorescenceintensity A. P. H. J. Schenning, E. W. Meijer, J. Am. Chem. Soc. , 2002, 124, 1269-1275

  28. Assembled by п-пinteraction Temperature-dependent CD (a), UV/vis (b), and fluorescence (c) spectra of 1 in n-butanol (2.6*10-5 mol.L-1). The last: Temperature-dependent CD spectra of 1 in water A. P. H. J. Schenning, E. W. Meijer, J. Am. Chem. Soc. , 2002, 124, 1269-1275

  29. Assembled by п-пinteraction The chirality of the monomers’ side chains imparts chirality to the aggregates • AFM phase image showing the preferential orientation of large ribbons on graphite. • STM topographic image showing the internal structure of a large ribbon on graphite. • AFM phase image on silicon, showing left-handed helical aggregates. A. P. H. J. Schenning, E. W. Meijer, J. Am. Chem. Soc. , 2002, 124, 1269-1275

  30. Assembled by п-пinteraction Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885–892

  31. Assembled by п-пinteraction Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885–892

  32. Assembled by п-пinteraction AFM image of a thin deposit on mica of (a) 1a from THF; (b) 1b from THF; (c) 1c from THF; (d) 1d from toluene. The scale bar represents 500 nm. Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885–892

  33. Assembled by п-пinteraction AFM images of conjugated chiral oligomers deposited on Si/SiOx: (a) 2a from toluene; (b) 2c from toluene; (c) and (d) 4c from THF. The scale bar represents 1.0 nm. • Polarity of the silicon plays an important role in the expression of chirality • Thermodynamic and kinetic control are also important Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885–892

  34. Assembled by п-пinteraction AFM images of: (a) 2a on graphite; (b) 2a on mica; (c) 3a on Si/SiOx; and (d) 3b on graphite. The scale bar represents 1.0 um. Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885–892

  35. Assembled by п-пinteraction Molecular structure of the oligo(p-phenylenevinylene) derivatives OPV-x [for OPV-3, y =1; OPV-4, y=2; and OPV-5, y=3] and schematic representation of the self-assembly process. Pascal Jonkheijm, E. W. Meijer, Science, 2006, 313, 80

  36. Assembled by п-пinteraction STM images of dimeric OPV4 monolayers on graphite(A) Image size is 12.1*12.1 nm2 (B) Molecular model representing the 2D ordering in A. STM image of mixed lamellae of OPV3 and OPV4 on a graphite surface from a concentrated 1,2,4-trichlorobenzene solution. A. Gesquiere, E. W. Meijer, Nano Lett., 2004, 4, 1175-1179

  37. Assembled by п-пinteraction Tapping mode AFM images (5*5um2) of OPV4 on substrates drop cast from heptane solutions (6.7*10-6 M) on graphite Pascal Jonkheijm, E. W. Meijer, J. Am. Chem. Soc., 2003, 125, 15949

  38. Assembled by п-пinteraction (D to F) Tapping-mode AFM images of self-assemblies of OPV-4 on graphite surfaces showing different degree of clustering depending on the concentration of the drop cast solution Pascal Jonkheijm, E. W. Meijer, J. Am. Chem. Soc., 2003, 125, 15949

  39. Assembled by п-пinteraction Temperature Polarity of solvent Symmetry of molecules Thermodynamic conditions Pascal Jonkheijm, E. W. Meijer, J. Am. Chem. Soc., 2003, 125, 15949

  40. Assembled by п-пinteraction Variable temperature measurements (heating ramp, steps of 10 K) (a) UV/vis (b) fluorescence and (c) CD spectra for OPV-4 in dodecane solution (14 μM). Pascal Jonkheijm, E. W. Meijer, Science, 2006, 313, 80

  41. Assembled by п-пinteraction Pascal Jonkheijm, E. W. Meijer, Science, 2006, 313, 80

  42. Assembled by п-пinteraction This opens the way to align these stacks so as to connect their ends to electrodes and study the electro-optical properties of these nanosized wires. Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885–892

  43. Outline • Introduction • Lessons from nature • Scientists’ efforts Assembled byhydrogen bond Assembled byп-пinteraction Assembled bymetal-ligand Scientists’ bionic results • Conclusion and outlook • Acknowledgement

  44. Assembled by metal-ligand • 1) High rational design predictability by simple variation of the size and shape of the building units. • 2) Large number and diversity of possible transition metal complexes. • Bond energies in the range of 15 ± 30 kcal.mol-1 per interaction that fall between those of the strong covalent bonds in classical macrocycles and the weak interactions. • 4) Excellent product yields inherent in the self-assembly process.

  45. Assembled by metal-ligand P. J. Stang, Chem. Eur. J., 1998, 4, 19-27

  46. Assembled by metal-ligand P. J. Stang, Chem. Eur. J., 1998, 4, 19-27

  47. Assembled by metal-ligand Near quantitative yields P. J. Stang, D. H. Cao, J. Am. Chem. Soc. 1995, 117, 6273 P. J. Stang, J. A. Whiteford, Res. Chem. Intermed. 1996, 22, 659.

  48. Assembled by metal-ligand Crystallographic data (left) Space-filling models (right) J. A. Whiteford, C. V. Lu, P. J. Stang, J. Am. Chem. Soc. 1997, 119, 2524

  49. Assembled by metal-ligand P. J. Stang, D. H. Cao, J. Am. Chem. Soc. 1997, 119, 5163.

  50. Assembled by metal-ligand Nanosized cavities. J. Manna, P. J. Stang, J. Am. Chem. Soc. 1996, 118, 8731.

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