Paul SCHUTZENBERGER

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1882 - 2007
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Paul SCHUTZENBERGER
(Strasbourg 1830- Mézy-sur-Seine1897)
Professeur au Collège de France
Chaire de Chimie Minérale (1876-1897) 1er
Directeur de lESPCI créée en 1882
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Paul Schutzenberger (1830-1897), professeur de
chimie (1855-1865)
à lÉcole Supérieure des Sciences Appliquées
de Mulhouse

créée en 1855
Collège Communal de Mulhouse (créé en 1812)
En 1819,
dans son rapport sur l'Exposition des Produits
Industriels , le Préfet exposait au Ministre de
l'Intérieur, l'utilité de la création d'une
chaire de chimie à Mulhouse. Emile Schlumberger
fit les démarches à Paris en vue de trouver un
Régent pour cette chaire Dulong et Thenard lui
recommandèrent Degenne, ancien élève de l'École
Normale Supérieure. Selon Gueneau de Mussy,
membre du Conseil Royal de l'Instruction
Publique, Degenne est très fort en physique et
en chimie et, de plus, il a toute la sagacité
nécessaire pour faire l'application de ses
connaissances aux Arts .   L'ouverture du
cours de chimie fut annoncée dans les Affiches
de Mulhouse le cours de chimie appliquée
aux Arts, commencera le 1er mars 1822... .    
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From the ATOM to the MOLECULE
MOLECULAR CHEMISTRY
Mastering the Organization of Molecular Matter
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MILESTONES in MOLECULAR CHEMISTRY
VITAMIN B12
UREA
1828
Friedrich Wöhler
Robert Woodward Albert Eschenmoser
1972(1976)
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CHEMISTRY BEYOND THE MOLECULE
SUPRAMOLECULAR CHEMISTRY
TO
MOLECULAR CHEMISTRY
FROM
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MOLECULAR RECOGNITION
INTERACTION for BINDING INFORMATION for
SELECTING
requires
geometrical interactional
COMPLEMENTARITY
PREORGANIZATION
SCHLOSS und SCHLÜSSEL LOCK and
KEY
Emil FISCHER 1894
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SUPRAMOLECULAR CHEMISTRY
SELF-ORGANIZATION
Beyond Pre-organization
From Molecular Recognition
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SELF-ASSEMBLY of the TOBACCO MOSAIC VIRUS
From 2130 protein subunits 1 molecule of
viral RNA
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PROGRAMMED CHEMICAL SYSTEMS
MOLECULAR PROGRAMME
SUPRAMOLECULAR OPERATION
PROCESSING via RECOGNITION ALGORITHM defined by
INTERACTION PATTERN
INFORMATION
stored in the COMPONENTS
for SPECIES OUTPUT
STAGES of INFORMATION INPUT
RECOGNITION GROWTH TERMINATION
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INTERMOLECULAR INTERACTIONS
for
SUPRAMOLECULAR SELF-ORGANIZATION
Electrostatic Interactions Hydrogen
Bonding Donor-Acceptor Interactions Van der Waals
Forces Metal Ion Coordination
Medium effects solvophobic
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SELF-ORGANIZATION
of INORGANIC ARCHITECTURES
BRICKS/COMPONENTS MOLECULES CONNECTIONS /
CEMENT METAL CATIONS
The metal cations process the molecular
information in the ligand molecules through the
coordination algorithm
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SELF-ASSEMBLY of INORGANIC GRIDS
With OCTAHEDRAL METAL CATION COORDINATION SITES
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2x2 Grids
ditopic ligand
metal ion
2x2 grid
2x2 Grids with Octahedrally Coordinated Metal
Ions
4 MX2
4
bis-terdentate ligand
metal salt
R H, Me, Ph M CoII, ZnII, NiII, CdII, CuII,
PbII
2x2 grid
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?2x2? GRID ARCHITECTURES
FUNCTIONAL SUPRAMOLECULAR DEVICES
for
Supramolecular Electronics
Multiple Redox States
Supramolecular Spintronics
Spin Crossover Triggered Processes
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Fe4L4(ClO4)8 a multiple switch
Three triggers
Three levels
Mössbauer spectra
Angew.Chem.Int.Ed.2000,39,2504-2507
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Mapping of Multilevel Supramolecular Electronic
Species
CITS Current Induced Tunneling Spectrsocopy
Topography
CoII4L4(BF4)8
10 nm
3 nm
Lines of 1D ordered CoII4L48 grids
Local Resolution of the CoII ions
Conductance Transmission Probability
on HOPG
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ADDRESSING the METAL CENTERS
of a 2x2
COBALT(II) GRID
Theory and Experiment
b)
DFT - Theorie
Experiment
DFT Calculations
a) DFT calculation of occupied orbitals within an
energy window between EF and -0.7 eV and the
electron density map in superposition with the
crystal structure data. b) (Upper row) 3D
representation of DFT-calculated electron density
maps within an energy window between EF and
-0.55 eV and between EF and -1 eV . (Lower
row) Central section of the measured CITS maps .

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SELF-ORGANIZATION of a 4x4 PbII16 GRID
Array from 8 Ligand Molecules and 16 Lead(II)
Cations
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NANOSCIENCE and NANOTECHNOLOGY
PROGRAMMED SELF-ORGANIZATION
Spontaneous but controlled generation of
well-defined large complex
organized functional
supramolecular architectures
A powerful alternative or complement to
NANOFABRICATION and NANOMANIPULATION
From FABRICATION to SELF-FABRICATION
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SELF-ORGANIZATION
by DESIGN with SELECTION
INFORMATION PROGRAMMING
DIVERSITYDYNAMICS
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SELF-RECOGNITION in HELICATE SELF-ASSEMBLY
Dynamic Combinatorial Library of Helical Metal
Complexes
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Dynamic Library of Circular Helicates
FeX2
Hasenknopf, B. Lehn, J.-M., Kneisel, B.O., Baum,
G. Fenske,D. Angew.Chem. Int. Ed. 1996, 35, 1838
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SUPRAMOLECULAR CHEMISTRY is a
DYNAMIC CHEMISTRY
due to the LABILITY / REVERSIBILITY
of NON-COVALENT
INTERACTIONS enabling the exchange,
incorporation and decorporation of the
molecular components of a supramolecular entity
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DYNAMIC CHEMISTRY
Dynamics of Chemical Reactions

• REACTIONAL

• MOTIONAL

Molecular Motions Nanomechanical Shape Changes,
Motors
CONSTITUTIONAL
Dynamic Modification of the Constitution of
Chemical Entities
CONSTITUTIONAL DYNAMIC CHEMISTRY
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SUPRAMOLECULAR CHEMISTRY
is a DYNAMIC CHEMISTRY
due to the REVERSIBILITY of NON-COVALENT
INTERACTIONS
IMPORT
DYNAMICS into
MOLECULAR CHEMISTRY
through REVERSIBLE COVALENT BONDS
CONSTITUTIONAL DYNAMIC CHEMISTRY
MOLECULAR as well as SUPRAMOLECULAR
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CDC
CONSTITUTIONAL DYNAMIC CHEMISTRY
To
SUPRAMOLECULAR CHEMISTRY
From
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CONSTITUTIONAL DYNAMIC CHEMISTRY
SUPRAMOLECULAR and MOLECULAR
DIVERSITY
generates DYNAMIC
enables the operation of SELECTION
search for BIOLOGICALLY ACTIVE
SUBTANCES self-organization of DYNAMIC
NANOSTRUCTURES
development of molecular and supramolecular
CONSTITUTIONAL DYNAMIC MATERIALS
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DYNAMERS MOLECULAR or SUPRAMOLECULAR POLYMERIC
MATERIALS exhibiting REVERSIBLE COMPONENT
EXCHANGE
BIODYNAMERS
Dynamic Analogs of Biopolymers
SUPRAMOLECULAR / NON-COVALENT
MOLECULAR / COVALENT
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SUPRAMOLECULAR / NON-COVALENT DYNAMERS
SUPRAMOLECULAR POLYMER CHEMISTRY
The chemistry of SUPRAMOLECULAR
POLYMERS of the entities generated by
POLYASSOCIATION of
COMPLEMENTARY MOLECULAR MONOMERS connected
through
NON-COVALENT INTERACTIONS
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SUPRAMOLECULAR POLYMERS
Building blocks
Homoditopic or heteroditopic
complementary monomers
Homotritopic monomer for branching/cross-linking
Monotopic units for end-capping
Linear polymerization

n
Cross-linking
End-capping control of molecular weight
distributions
m
m
(m lt n)
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SUPRAMOLECULAR LIQUID CRYSTALLINE POLYMERS

from CHIRAL COMPLEMENTARY MOLECULAR COMPONENTS
A
O
H
N
O
D
O
H
N
O
R
O
N
R
O
O
A
H
D
O
N
H
O
O
N
O


H
N
O

O
N
O

O
H
A
O
O
R
O
O
R
N
N
H
O
D
N
H
O
O
Z
N
H
O
N
O
R
O
N
H

H
N
O

O
O
R
N
Z
O
N
H
O
R C12H25
Z CH3
Advanced Materials, 1990, 2, 254
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SUPRAMOLECULAR POLYMER formed via SEXTUPLE
HYDROGEN BONDING between Molecular
Monomers bearing Complementary Recognition
Groups
Études Physiques Sauveur-Jean Candau
Éric Buhler
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REVERSIBLE REACTIONS
AMINE CARBONYL CONDENSATIONS
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MOLECULAR / COVALENT DYNAMERS
POLYCONDENSATION of
FUNCTIONAL COMPLEMENTARY MONOMERS through

REVERSIBLE COVALENT CONNECTIONS
dialdehyde dihydrazide
polyacylhydrazone
diamine
polyimine
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THE ACYL HYDRAZONE GROUP
AMIDE
TWO SUBUNITS
IMINE
REVERSIBILITY
TWO FEATURES
HYDOGEN BONDING
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POLY ACYL HYDRAZONES
BIOPOLYMERS
MATERIALS
DYNAMIC BIOPOLYMERS
DYNAMIC POLYAMIDES
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POLY ACYL HYDRAZONES
DYNAMIC POLYAMIDES
A very strong flexible dynamer film
Tadahito NOBORI, MitsuiChemicals Inc.

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Water-desintegrative film based on a Dynamer
containing imine groups ( 20 cm x 60 m x
30 µ )
DYNAMER FILM
20 tons dynamer prepared
T. Nobori et al.,Mitsui Chemicals, 2006
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Silicone-derived Covalent Dynamer DYNASIL

H2O
n
Very Soft Stretchy Film
Developed by Takashi Ono, Shunsuke FUJII, Mitsui
Chemicals Inc.
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Soft-to-Hard Transformation of the Mechanical
Properties of a Covalent Dynamer by Incorporation
of Monomers
Hard Monomers
Very Soft Stretchy Film
C
A
B
n
D
A
D
D
A
B
A
C
A
B
B
A
A
B
C
A
B
D
A
B
60, 24h, in CHCl3
50mol
Soft Stretchy Film
25mol
75mol
Conversion of a Soft Stretchy Film into a
Hard Tough Film by Dynamic Exchange
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DYNAMIC POLYMER BLENDS
Schematic representation of crossover component
recombination between neat films of
polyacylhydrazone dynamers
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OPTO DYNAMIC POLYMERS
smart optical materials responsive to external
stimuli
Color and fluorescence changes of dynamic
polymers induced by bond
recombination and component exchange
Exchange reaction through the interface of two
different dynamic polymers
color
fluorescence
heated in oven
two dynamic polymer films are superimposed
color and fluorescence changed only where
superimposed
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Concept introducing a difference in degree of
conjugation by bond recombination
extended local conjugation
no conjugation
N
N
N
C
C
N
H
H
exchange reaction
no conjugation
weak local conjugation
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The two polymer films are cut with scissors and
superimposed
color
fluorescence
under 365nm
heated at 170C
for 5min
yellow color only where superimposed
yellow-green fluorescence only where superimposed
In this case, both polymer films are formed using
a mixed solvent (CHCl3/DMF). Both films are soft
and relatively stretchy containing 9-10wt of
DMF.
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SELECTION in a CONSTITUTIONAL DYNAMIC LIBRARY




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CONSTITUTIONAL DYNAMIC SELF-SENSING
Fluorescence Spectra of the Dynamer Library as a
function of
added ZnII cations




Component Exchange
Sensing
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CONSTITUTIONAL DYNAMIC CHEMISTRY
MOLECULARSUPRAMOLECULAR
DYNAMIC CONSTITUTIONAL DIVERSITY

• chemical systems undergoing continuous

recomposition/recombination/reorganization under
the
pressure of internal
factors
external

• deconstruction and reconstruction

SELECTION through Dynamic Constitutional
Diversity responding to the pressure of
internal/external factors
Novel Paradigm
ADAPTATION
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PREORGANISATION
SELF-ORGANISATION
Diversity Dynamics
Information Programming
DESIGN
DESIGN
SELECTION
SUPRAMOLECULAR CHEMISTRY
CONSTITUTIONAL DYNAMIC CHEMISTRY
MOLECULAR CHEMISTRY
Constitutional
Dynamics
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CDC
CONSTITUTIONAL DYNAMIC CHEMISTRY
MOLECULAR
SUPRAMOLECULAR
ADAPTIVE EVOLUTIVE CHEMISTRY
DARWINIAN !
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