self-assembly in supramolecular chemistry -- inspiration from nature

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Self-Assembly In Supramolecular Chemistry

-- Inspiration From Nature

Reporter: Zhengming Tang

唐铮铭 Supervisor ： Prof. Jian Pei

2006.11.3

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Outline

Introduction Lessons from nature Scientists’ efforts Conclusion and outlook Acknowledgement

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Outline

Introduction Lessons from nature Scientists’ efforts Conclusion and outlook Acknowledgement

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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.

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Introduction

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

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Outline

Introduction Lessons from nature Scientists’ efforts Conclusion and outlook Acknowledgement

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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

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Lessons from nature--AQP1selective water permeation

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

Hydrophobic effects

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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.

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Lessons from nature--light-harvesting protein PE545

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

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Lessons from nature--DNA bound by base pairs

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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

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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

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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

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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

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The essence of hydrogen bond

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

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Assembled by hydrogen bond

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

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

Assembled by hydrogen bond

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Design strategy

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

Assembled by hydrogen bond

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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

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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

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Assembled by hydrogen bond

Supramolecular peapods

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

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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

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Assembled by п-п interaction

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

Some simple models:

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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

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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

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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

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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

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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

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

Assembled by п-п interaction

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Assembled by п-п interaction

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

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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.

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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

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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.

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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

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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

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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

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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

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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

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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

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Assembled by п-п interaction

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

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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

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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

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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.

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Assembled by metal-ligand

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

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Assembled by metal-ligand

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

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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

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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

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Assembled by metal-ligand

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

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Assembled by metal-ligand

Nanosized cavities.

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

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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.

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Assembled by metal-ligand

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

Octahedron by 3-D assembly

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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

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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

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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.

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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

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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.

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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:

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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.

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Assembled by metal-ligandAFM, TEM, UHV-STM

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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

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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

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Scientists’ bionic results

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

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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

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Conclusion and outlook

Characterization

Application

ModelLab result

Design

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Conclusion and outlook

Plastic transitors, photovoltaics, molecular machine,nano-devices

Bionic system

Biosystem…

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Acknowledgement

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

Other professors in Organic Institute

All members in our lab

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Thanks for your attention !Thanks for your attention !