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Master 1 CMS, 2016, N. GiusepponeIntroduction to Supramolecular Chemistry

Further Readings

Introduction to Supramolecular Chemistry

H2N NH2

OH2N NH2

OH2N Me

OH2N H

MeHHHHHH

MeH Me H H

Me Me H H

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

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

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

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.

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)

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

Valinomycin

Pedersen Lehn Cram

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 interactions

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

Concepts: Supramolecular interactions

Thermodynamics of the host-guest association

Concepts in Supramolecular Chemistry

Complementarity and preorganization

K = 2.5 1013 M-1 K = 9.3 103 M-1 K = 1060 M-1

Types of Preorganization

The Chelate Effect

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

T.J. Murray, S.C. Zimmerman, J. Am. Chem. Soc. 1992, 114, 4010.

Zimmerman Anslyn

Wisner

Drop by 109-foldwhen adding a noncomplementary interaction

Size and shape

J.-M. Lehn et al, J. Am. Chem. Soc. 1975, 97, 6700.

Size and shape

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

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)]

Aminoester resolving machine

Macrocyclesand spherands

Macrocycles

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

Template Synthesis

Templated Catalysis

Template Synthesis and Self-replication

Chimie Supramoléculaire

V. Rotello, J.-I. Hong, and J. Rebek, Jr.,J. Am. Chem. Soc.,1991, 113, 9422–9423.

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