self-assembly in supramolecular chemistry -- inspiration from nature

68
1 Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature Reporter: Zhengming Tang 唐唐唐 Supervisor Prof. Jian Pei 2006.11.3

Upload: olin

Post on 20-Jan-2016

51 views

Category:

Documents


2 download

DESCRIPTION

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 - PowerPoint PPT Presentation

TRANSCRIPT

Page 1: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

1

Self-Assembly In Supramolecular Chemistry

-- Inspiration From Nature

Reporter: Zhengming Tang

唐铮铭 Supervisor : Prof. Jian Pei

2006.11.3

Page 2: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

2

Outline

Introduction Lessons from nature Scientists’ efforts Conclusion and outlook Acknowledgement

Page 3: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

3

Outline

Introduction Lessons from nature Scientists’ efforts Conclusion and outlook Acknowledgement

Page 4: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

4

Introduction

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, 2400Freek J. M. Hoeben, E. W. Meijer, Chemical Reviews 2005, 105, 1491

Nobel Prize in 1987: Pederson C , Cram D J, Lehn J M.

Page 5: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

5

Introduction

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

Page 6: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

6

Outline

Introduction Lessons from nature Scientists’ efforts Conclusion and outlook Acknowledgement

Page 7: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

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

Page 8: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

8

Lessons from nature--AQP1selective water permeation

Kazuyoshi Murata, Kaoru Mitsuoka, Teruhisa Hirai, Nature 2000, 407, 599-605.

Hydrophobic effects

Page 9: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

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 Materials 2006, 5, 683-696.

Page 10: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

10

Lessons from nature--light-harvesting protein PE545

Centre for Quantum Information and Quantum Control, University of Toronto,Nature Materials 2006, 5, 683-696.

Page 11: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

11

Lessons from nature--DNA bound by base pairs

Page 12: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

12

Outline Introduction Lessons from nature Scientists’ efforts Assembled by hydrogen bond Assembled by п-п interaction Assembled by metal-ligand Scientists’ bionic results

Conclusion and outlook Acknowledgement

Page 13: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

13

Outline Introduction Lessons from nature Scientists’ efforts Assembled by hydrogen bond Assembled by п-п interaction Assembled by metal-ligand Scientists’ bionic results

Conclusion and outlook Acknowledgement

Page 14: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

14

Scientists’ efforts Assembled by hydrogen bond

“The discovery of the Hydrogen Bond could have won someone the Nobel Prize, but it didn’t.” George A. Jeffrey, Wolfram Saenger, 1991

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

Page 15: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

15

The essence of hydrogen bond

1) Electrostatic or coulomb energy (Δ ECOU)

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

Page 16: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

16

The essence of hydrogen bond

Felix H. Beijer, E. W. Meijer, J. Am. Chem. Soc. 1998, 120, 6761-6769

Page 17: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

17

Assembled by hydrogen bond

Takashi Kato, Norihiro Mizoshita, Angew. Chem. Int. Ed. , 2006, 45, 38– 68.

Page 18: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

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

Assembled by hydrogen bond

Page 19: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

19

Design strategy

T. Yamaguchi, Takuzo Aida, J. Am. Chem. Soc. 2003, 125, 13934-13935

Assembled by hydrogen bond

Page 20: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

20

TEM micrographs of (a,b) 1acid with C60

(c,d) 1acid alone.T. Yamaguchi, Takuzo Aida, J. Am. Chem. Soc. 2003, 125, 13934-13935

Assembled by hydrogen bond

Page 21: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

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

Page 22: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

22

Assembled by hydrogen bond

Supramolecular peapods

T. Yamaguchi, Takuzo Aida, J. Am. Chem. Soc. 2003, 125, 13934-13935

Page 23: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

23

Outline Introduction Lessons from nature Scientists’ efforts Assembled by hydrogen bond Assembled by п-п interaction Assembled by metal-ligand Scientists’ bionic results

Conclusion and outlook Acknowledgement

Page 24: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

24

Assembled by п-п interaction

M. O. Sinnokrot, C. David Sherrill, J. Am. Chem. Soc. 2004, 126, 7690-7697

Some simple models:

Page 25: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

25

Assembled by п-п interaction

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, 6916-6924Rene A. J. Janssen, Jean M. J. Frechet, Macromolecules, 2000, 33, 7038-7043

Page 26: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

26

Assembled by п-п interaction

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 excitedat 2.11 eV, dashed lines) G3-T17-G3 in dichloromethane.

Joke J. Apperloo, Rene A. J. Janssen, J. Am. Chem. Soc., 2001, 123, 6916-6924Rene A. J. Janssen, Jean M. J. Frechet, Macromolecules, 2000, 33, 7038-7043

Page 27: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

27

Assembled by п-п interaction

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 fluorescence intensity

A. P. H. J. Schenning, E. W. Meijer, J. Am. Chem. Soc. , 2002, 124, 1269-1275

Page 28: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

28

Assembled by п-п interaction

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

Page 29: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

29

Assembled by п-п interaction

a) AFM phase image showing the preferential orientation of large ribbons on graphite.b) STM topographic image showing the internal structure of a large ribbon on graphite.c) 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

The chirality of the monomers’ side chains imparts chirality to the aggregates

Page 30: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

30Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885–892

Assembled by п-п interaction

Page 31: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

31

Assembled by п-п interaction

Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885–892

Page 32: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

32

Assembled by п-п interaction

Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885–892

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.

Page 33: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

33

Assembled by п-п interaction

AFM images of conjugated chiral oligomers deposited on Si/SiOx: (a) 2a from toluene; (b) 2c from toluene; (c) and (d) 4c fromTHF. The scale bar represents 1.0 nm.

1) Polarity of the silicon plays an important role in the expression of chirality

2) Thermodynamic and kinetic control are also important

Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885–892

Page 34: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

34

Assembled by п-п interaction

Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885–892

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.

Page 35: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

35

Assembled by п-п interaction

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

Page 36: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

36

Assembled by п-п interaction

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

Page 37: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

37

Tapping mode AFM images (5*5um2) of OPV4 on substrates drop cast from heptane solutions (6.7*10-6 M) on graphite

Assembled by п-п interaction

Pascal Jonkheijm, E. W. Meijer, J. Am. Chem. Soc., 2003, 125, 15949

Page 38: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

38

Assembled by п-п interaction

(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

Page 39: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

39

Assembled by п-п interaction

Pascal Jonkheijm, E. W. Meijer, J. Am. Chem. Soc., 2003, 125, 15949

Temperature

Polarity of solvent

Symmetry of molecules

Thermodynamic conditions

Page 40: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

40

Assembled by п-п interaction

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

Page 41: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

41

Assembled by п-п interaction

Pascal Jonkheijm, E. W. Meijer, Science, 2006, 313, 80

Page 42: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

42

Assembled by п-п interaction

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

Page 43: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

43

Outline Introduction Lessons from nature Scientists’ efforts Assembled by hydrogen bond Assembled by п-п interaction Assembled by metal-ligand Scientists’ bionic results

Conclusion and outlook Acknowledgement

Page 44: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

44

Assembled by metal-ligand1) High rational design predictability by simple variation of th

e size and shape of the building units.

2) Large number and diversity of possible transition metal complexes.

3) 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.

Page 45: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

45

Assembled by metal-ligand

P. J. Stang, Chem. Eur. J., 1998, 4, 19-27

Page 46: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

46

Assembled by metal-ligand

P. J. Stang, Chem. Eur. J., 1998, 4, 19-27

Page 47: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

47

Assembled by metal-ligand

P. J. Stang, D. H. Cao, J. Am. Chem. Soc. 1995, 117, 6273P. J. Stang, J. A. Whiteford, Res. Chem. Intermed. 1996, 22, 659.

Near quantitative yields

Page 48: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

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

Page 49: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

49

Assembled by metal-ligand

P. J. Stang, D. H. Cao, J. Am. Chem. Soc. 1997, 119, 5163.

Page 50: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

50

Assembled by metal-ligand

Nanosized cavities.

J. Manna, P. J. Stang, J. Am. Chem. Soc. 1996, 118, 8731.

Page 51: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

51

Assembled by metal-ligandTwelve units come together precisely with high yield: A Remarkable reaction

P. J. Stang, N. E. Persky, J. Manna, J. Am. Chem. Soc. 1997, 119, 4777.

Page 52: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

52

Assembled by metal-ligand

P. J. Stang, B. Olenyuk, D. C. Muddiman, Organometallics, 1997, 16, 3094.

Octahedron by 3-D assembly

Page 53: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

53

Assembled by metal-ligand

In fact the real challenges, as in all of contemporary supramolecular chemistry, are the proper characterization and structure determination of the species observed. This challenge increases with the complexity of the supramolecular species, from simple polygons (triangles and squares) to complex polyhedra (cuboctahedron, dodecahedron, etc.).

P. J. Stang 1998

Page 54: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

54

Assembled by metal-ligand

i) N-ethylmorpholine, MeOH, 12 h, reflux; b) methanolic NH4PF6

George R. Newkome, Tae Joon Cho, Chem. Eur. J. 2002, 8, 2946-2954

Molecular modeling:D=3.7 nm

Page 55: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

55

Assembled by metal-ligand

George R. Newkome, Tae Joon Cho, Chem. Eur. J. 2002, 8, 2946-2954

Transmission electron micrograph of 18+12.12PF6 (magnification of 200000) showing an individual, regular hexagon.

Page 56: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

56

Assembled by metal-ligand

George R. Newkome, Pingshan Wang, et al., Science, 2006, 312, 1783

Sierpinski’s hexagonal gasket synthesized by Newkome

Energy minimization calculations

12.3 nm in diameter and 0.7 nm in height

Page 57: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

57

Assembled by metal-ligandSynthetic route:

(a) 1 and 2 were mixed with N-ethylmorpholine in refluxing CH3OH/CHCl3

(2:1 v/v), for 20 hours.(b) 3 and 4 were stirred in refluxing CH3OH with added N-ethylmorpholine for 12 hours.

Page 58: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

58

Assembled by metal-ligand

(c) First, hexamer 5 was refluxed in CH3OH in the presence of 1 equiv. of FeCl2.6H2O for 20 hours. Then, to a CH3OH solution of 5(Cl– )m(NO3

–)n was added a solution of NH4PF6 to obtain the desired gasket 6 as a precipitate.

c

Synthetic route:

Page 59: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

59

Assembled by metal-ligandFull characterization of hexagonal gasket molecule :

H1NMR: 9.45 ppm attributed to the tpy-Fe-tpy complex and the other at 9.20 ppm attributed to the tpy-Ru-tpy complex, displaying the requisite1:6 integration.

UV-vis: the absorbance pattern at 575 and 495 nm with a 1:6 ratio for the tpy-Fe-tpy and tpy-Ru-tpy units, respectively.

MALDI-TOF MS: failed to provide definitive structural information due to overall 84+ molecular charge.

Page 60: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

60

Assembled by metal-ligandAFM, TEM, UHV-STM

Page 61: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

61

Outline Introduction Lessons from nature Scientists’ efforts Assembled by hydrogen bond Assembled by п-п interaction Assembled by metal-ligand Scientists’ bionic results

Conclusion and outlook Acknowledgement

Page 62: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

62

Scientists’ bionic results

Nucleotide-Appended Thymine (T)

Adenine Nucleotide (A) )

R. Iwaura, E. W. Meijer, T. Shimizu, J. Am. Chem. Soc. 2006, 128, 13298-13304

Page 63: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

63

Scientists’ bionic results

R. Iwaura, E. W. Meijer, T. Shimizu, J. Am. Chem. Soc. 2006, 128, 13298-13304

Page 64: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

64

Scientists’ bionic results

Left: (a,b,c) AFM images for the binary self-assembly of (T:A=1:1 ), 1.8*10-2 M/1.8*10-3 M).

Right-handed DNA-like nanofibers

Right: (a, b) AFM images for the binary self-assembly from of (T:A=2:1, 1.8*10-2 M/9*10-4 M).

R. Iwaura, E. W. Meijer, T. Shimizu, J. Am. Chem. Soc. 2006, 128, 13298-13304

Page 65: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

65

Conclusion and outlook

Characterization

Application

ModelLab result

Design

Page 66: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

66

Conclusion and outlook

Plastic transitors, photovoltaics, molecular machine,nano-devices

Bionic system

Biosystem…

Page 67: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

67

Acknowledgement

Prof. Jian Pei, Prof. Yuguo Ma, Prof. Dahui Zhao

Other professors in Organic Institute

All members in our lab

Page 68: Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

68

Thanks for your attention !Thanks for your attention !