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Master 1 CMS, 2016, N. GiusepponeIntroduction to Supramolecular Chemistry
Further Readings
Introduction to Supramolecular Chemistry
H
H2N NH2
ON
Me
O
N
N N
N
Me
Me
OH2N NH2
O
NH2
OMeMe
O
NH2
H
HH
OH2N Me
MeH
OH2N H
O
NH
MeP
OO O
HOH
H
H H
N
NMe
MeMe
Co
CN
OHO
O
O
O
O
O
O
O O
O O
HO
CHO
H
H
H
MeHHHHHH
O
MeH Me H H
Me Me H H
H
Me
Me
OOO
O
OO
H
t-BuH
HO
MeHO
HHO
O
Urea(Wöhler, 1828)
Tropinone(Robinson, 1917)
Vitamin B12(Woodward, 1973)
Brevetoxin B(Nicolaou, 1995)
Ginkgolide B(Corey, 1988)
Some key achievements using the covalent bond formation
Concepts: Generalities
Master 1 CMS, 2016, N. Giuseppone
Currently in progress…
Concepts: Generalities
Introduction to Supramolecular Chemistry Master 1 CMS, 2016, N. Giuseppone
Introduction to Supramolecular Chemistry
The Supramolecular Approach
Supramolecular chemistry is the chemistry beyond the moleculethat is the chemistry of molecular assemblies and of the intermolecular bond
J.-M. Lehn, Supramolecular Chemistry – Concepts and Perspectives, Wiley-VCH Verlag GmbH, Weinheim, 1995.J.-M. Lehn, Angew. Chem. Int. Ed. Engl. 1988, 27, 89.
The early work in the field concerned the formation of « supermolecules »comprising two components, a host and a guest, which interact with one anotherIn a non-covalent manner
Master 1 CMS, 2016, N. Giuseppone
The host-guest relationship has been definedby Donald CramD.J. Cram, Angew. Chem. Int. Ed. Engl. 1986, 25, 1039.
Complexes are composed of two or more molecules or ionsheld together in unique structural relationships by electrostaticforces other than those of full covalent bonds … molecularcomplexes are usually held together by hydrogen bonding,by ion pairing, by π-acid to π-base interactions, bymetal-to-ligand binding, by van der Waals attractive forces,by solvent reorganising, and by partially made and brokencovalent bonds (transition states)…High structural organisationis usually produced only through multiple binding sites… A highly structured molecularcomplex is composed of at least one host and one guest component… A host–guestrelationship involves a complementary stereoelectronic arrangement of binding sites inhost and guest… The host component is defined as any organic molecule or ion whosebinding sites converge in the complex… The guest component as any molecule or ionwhose binding sites diverge in the complex…
Supramolecular Self-assemblies in Nanotechnologies
The Supramolecular Approach
Master 1 CMS, 2016, N. Giuseppone
Fundamentally, supramolecular chemistryconcerns mutual interactions of molecules ormolecular entities with discrete properties andwhich come together either spontaneously or bydesign
We can trace the evolution from the originalsolid-state « clathrate », through the in solutionmolecular host-guest complex and to the self-assembly paradigm.
Supramolecular Self-assemblies in Nanotechnologies
The Supramolecular Approach
Master 1 CMS, 2016, N. Giuseppone
Supramolecular Self-assemblies in Nanotechnologies
The Supramolecular Approach
Master 1 CMS, 2016, N. Giuseppone
Emil Fischer(1852 - 1919)
Illustrative timeline of the development of host-guest interactions1810- Sir Humphrey Davy: discovery of chlorine hydrate1823- Michael Faraday: formula of chlorine hydrate1849- Friedrich Wöhler: -quinol H2S clathrate1893- Alfred Werner: coordination chemistry (bindingattration – mutual affinity)1894- Lock and key concept by Emil Fischer(binding must be selective / complementarity of geometry /steric fit / molecular recognition)1906- Paul Ehrlich introduce the concept of biologicalreceptor (molecules do not act if they do not bind)
Supramolecular Self-assemblies in Nanotechnologies
The Supramolecular Approach
Master 1 CMS, 2016, N. Giuseppone
Illustrative timeline of the development of host-guest interactions1937- K.L. Wolf: the term of supermolecule is used to discribe acetic acid dimers1939- L. Pauling: Hydrogen bonds are included in the Nature of the chemical bond1945- H.M. Powell: X-ray structure of -quinol inclusion compounds1953- Watson and Crick: structure of DNA1967- Charles Pedersen: Crown ethers1969- Jean-Marie Lehn: First cryptands1973- Donald Cram: Preorganization in spherands1978- The term of supramolecular chemistry
is introduced by Lehn1987- Award of the Nobel Prize
Supramolecular Self-assemblies in Nanotechnologies
The Supramolecular Approach
Master 1 CMS, 2016, N. Giuseppone
Valinomycin
Pedersen Lehn Cram
The Supramolecular Approach
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
The nature of the supramolecular bond J.W. Steed, J.L. Atwood, Supramolecular Chemistry,2nd Ed. John Wiley and Sons, Chichester, 2009.
Supramolecular Self-assemblies in Nanotechnologies
Supramolecular interactions
Master 1 CMS, 2016, N. Giuseppone
Hydrogen bonds can present various lengths, strengths, and geometries
G.A. Jeffrey, An introduction to hydrogen bonding,Oxford University Press, New York, 1997.
Supramolecular interactions
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Introduction to Supramolecular Chemistry
Concepts: Supramolecular interactions
Thermodynamics of the host-guest association
Master 1 CMS, 2016, N. Giuseppone
Concepts in Supramolecular Chemistry
Complementarity and preorganization
K = 2.5 1013 M-1 K = 9.3 103 M-1 K = 1060 M-1
Fe3+
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Preorganization
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
The Chelate Effect
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
The Chelate Effect
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
The Chelate Effect
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
The Chelate Effect
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Complementarity
Multiple hydrogen bonds and secondary electrostatic interactions
W.L. Jorgensen, J. Pranata, J. Am. Chem. Soc. 1990, 112, 2008.
Theoretical prediction
Cyclohexylthymine / 9-ethyladenineCyclohexylthymine/AminoadenineCytidine derivatve/Guanosine derivative
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Complementarity
T.J. Murray, S.C. Zimmerman, J. Am. Chem. Soc. 1992, 114, 4010.
Zimmerman Anslyn
Wisner
Leigh
Drop by 109-foldwhen adding a noncomplementary interaction
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Preorganization
Size and shape
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Preorganization
Size and shape
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Preorganization
Size and shape
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Preorganization
Size and shape
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Complementarity
J.-M. Lehn et al, J. Am. Chem. Soc. 1975, 97, 6700.
Size and shape
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Complementarity
Size and shape
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Complementarity
Size and shape
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Preorganization
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Complementarity
J. Am. Chem. Soc. 2005, 127, 15959, J. Am. Chem. Soc. 2004, 126, 5806, and J. Am. Chem. Soc. 2010, 132, 4445.
Size and shape
Ka = 4.5 108M-1
37: 86 Å3 ; Ka = 3 105M-1
38: 89 Å3 ; Ka = 3 102M-1
39: Ka = 1.3 103M-1
40a: Ka < 140b: Ka < 1
V = 474 Å3 V = 272 Å3
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Complementarity
D.J. Cram, et al., J. Am. Chem. Soc. 1973, 95, 2692.
Spatial complementarity and chirality
30 kJ.mol-1 => e.e. = 50%80 kJ.mol-1 => e.e. = 90%
100 kJ.mol-1 => e.e. = 95%145 kJ.mol-1 => e.e. = 99%
G = ln[(100+ee)/(100-ee)]
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Complementarity
Spatial complementarity and chirality
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Complementarity
D.J. Cram, et al., J. Am. Chem. Soc. 1979, 101, 4941.
Spatial complementarity and chirality
Time
Chr
omat
ogra
phy
colu
mn
Aminoester resolving machine
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Complementarity
Spatial complementarity and chirality
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Preorganization
D.J. Cram, et al., J. Am. Chem. Soc. 1979, 101, 4941.
Macrocyclesand spherands
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Preorganization
Supramolecular Self-assemblies in Nanotechnologies
Concepts in Supramolecular Chemistry
Master 1 CMS, 2016, N. Giuseppone
Types of Preorganization
Macrocycles
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Types of Preorganization
Desolvation
Meijer’s ureidopyrimidinone
Ka > 106 M-1
Meijer et al., J. Am. Chem. Soc. 1998, 120, 6761. Diederich et al., J. Am. Chem. Soc. 1990, 112, 339.
CS2 ………………………H2O
- 9.4 kcal.mol-1- 1.3 kcal.mol-1
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Template Synthesis
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Template Synthesis
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Template Synthesis
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Template Synthesis
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Template Synthesis
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Templated Catalysis
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire Master 1 CMS, 2016, N. Giuseppone
Template Synthesis and Self-replication
Concepts in Supramolecular Chemistry
Chimie Supramoléculaire
V. Rotello, J.-I. Hong, and J. Rebek, Jr.,J. Am. Chem. Soc.,1991, 113, 9422–9423.
Master 1 CMS, 2016, N. Giuseppone