Autoassemblage Hosseini

8/4/2019 Autoassemblage Hosseini

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Assemblage et Auto-assemblage Molculaire

Professeur M. Wais Hosseini

Institut Universitaire de France (IUF)

Universit Louis Pasteur

UMR CNRS 7140

Master de Chimie Molculaire et Supramolculaire


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Rfrences Bibliographiques

Chimie Supramolculaire

Lehn, J.-M. Supramolecular Chemistry, Concepts and Perspectives, VCH, Weinheim,

1995.

Ingnierie de l'tat cristallin

G. D. Desiraju, Crystal Engineering: The Design of Organic Solids, Elsevier, New

York, 1989.

Auto-assemblage

J. S. Lindsey,New J. Chem. 1991, 15, 153.

Tectonique molculaire

Hosseini, M. W. Tectonique molculaire: de tectons simples aux rseaux

molculaires complexes,Actualit Chimique., 2005, 290-291, 59.

Simard, M.; Su, D.; Wuest, J. D. Use of Hydrogen Bonds to Control Molecular

Aggregation. Self-Assembly of Three Dimensional Networks with Large Chambers.J.

Amer. Chem. Soc., 1991, 113, 4696.

Mann, S.Molecular tectonics in biomineralization and biomimetic materials

chemistry.Nature, 1993, 365, 499.M. W. Hosseini,Reflexion on Molecular Tectonics, Cryts. Eng. Comm., 2004, 6, 318.

M. W. Hosseini, Molecular tectonics: from simple tectons to complex molecular

networks,Acc. Chem. Res., 2005, 38, 313.


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Rseaux par inclusion: Hosseini, M. W.; De Cian, A.Molecular Tectonics: An

Approach to Organic Networks. Chem. Comm. 1998, 727.

Rseaux par liaison hydrogne: Taylor, R.; Kennard, O.Hydrogen-Bond Geometry in

Organic Crystals.Acc. Chem. Res., 1984, 17, 320.Etter, M.C. Encoding and Decoding Hydrogen-Bond Patterns of Organic Compound.

Acc. Chem. Res., 1990, 23, 120.

C. B. Aakery, K. R. Seddon, Chem. Soc. Rev., 1993, 22, 397.

Subramanian, S.; Zaworotko, M. J.Exploitation of the hydrogen bond: recent developments

in the context of crystal engineering. Coord. Chem. Rev., 1994, 137, 357.

G. R. Desiraju,Angew. Chem. Int. Ed. Engl., 1995, 34, 2311.

Lawrence, D. S.; Jiang, T.; Levett, M. Self-Assembling Supramolecular Complexes. Chem.Rev., 1995, 95, 2229.

J. F. Stoddart, D. Philip, Self-Assembly in Natural and UnnaturalSystems.Angew. Chem.

Int. Ed. Engl., 1996, 35, 1154.

Fredericks, J. R.; Hamilton, A. D. in Comprehensive Supramolecular Chemistry, Eds J. L.

Atwood, J. E. Davis, D. D. Macnico, F. Vgtle, Vol. 9 (Eds. J. P. Sauvage, M. W. Hosseini,

Elsevier, Oxford, 1996, pp. 565.

Braga,D.; Grepioni, F. Intermolecular Interactions in non Organic Crystal Engineering.Acc. Chem. Res., 2000, 33, 601.

Holman, K. T.; Pivovar, A. M.; Swift, J. A.; Ward,M. D. Metric Engineering of

SoftMolecular Host Frameworks.Acc. Chem. Res., 2001, 34, 107.

Hosseini, M. W.,Molecular tectonics : from molecular recognition of anions to molecular

networks, Coord. Chem. Rev., 2003, 240, 157.


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Rseaux par liaison de coordination

Batten, S. R.; Robson, R.Interpenetrating Nets: Ordered Periodic Entanglement.

Angew. Chem. Int. Ed., 1998, 37, 1460.

Blake, A. J.; Champness, N. R.; Hubberstey, P.; Li, W.-S.; Withersby, M. A.; Schrder,

M.Inorganic Crystal Engineering using Self-Assembly of Tailored Building-Blocks.

Coord. Chem. Rev., 1999, 183, 117.

Hosseini, M. W.An Approach to the Crystal Engineering of Coordination Networks. in

Crsytal Engineering: From Molecules and Crystals to Materials, NATO ASI Series,

Eds. D. Braga, F. Grepioni, G. Orpen, Serie c, Kluwer, Dordrecht, Netherlands, 1999,

538, 181.

Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.; O'Keeffe, M.; Yaghi, O.

M.Modular Chemistry: Secondary Building Blocks as a Basis for the Design of Hoghly

Porous and Robust Metal-Organic Carboxylate Frameworks.Acc. Chem. Res., 2001,

34, 319.

Moulton, B.; Zaworotko, M.J. From Molecules to Crystal Engineering:

Supramolecular Isomerism and Polymorphism in Network Solids. Chem. Rev. 2001,

101, 1629.


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An Ensemble of Disordered InertConstruction Units (non-informed)

Periodic Archtecture

External interventionsequential construction process

Low probabilityin the absence of external intervention

Self-assembly :A sequential builiding process

Disordered Ensemble ofActive Construction units (informed)

Tectons Recognition Patterns

Molecular Tectonics : From Tectons to Networks


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Molecular Tectonics : Search for Energy minima

Recognitionpatterns


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E

A B C D E

A B

C DE

Molecular Tectonics : Search for Energy minima


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Directional

Non Directional

Polar Apolar

Apolar

Directional and Non Directional Arrangements


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From Tectons to Molecular Networks

Tectons

xy

zx

y

z

NT1T2 A1

1 2

CF1F2 A1

0 2

2 x 2 4 x 4 4 x 4

NT1T2 A1

2 2xy

z


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Molecular Tectonics

F r o m A t o m s t o t e c t o n s, f r o m t e c t o n s t o M o l e c u la r N e t w o r k s

Molecular Synthesis

Tecton (T)Atoms

Supramolecular Synthesis

Complementaryinteraction sites

Self-complementary

NT A

2 1

Network

Self-assembly

Recognition pattern (A)

Molecular Recognition and Repetition

I n t e r p la y b e t w e e n s t rong (K inet i c a l l y i ner t ) and w e a k (k inet i c a l l y l ab i l e ) I n terac t i ons

Configurationally Robust(Invariance of atomic connectivity)

Non-Covalent BondIntertecton Links

Covalent BondInteratomic interactions


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Molecular Tectonics

Molecular Synthesis

Complementary Tectons

AtomsTecton (T2) Tecton (T1)

Interatomic Link byCovalent Bond (Non reversible)


Tecton (T)

Self-Complementary Tecton

Supramolecular Synthesis Conservation of ConfigurationNon-Covalent BondIntertecton Link (A)

Networks

Complementary Tectons

NT1T2 A

1 2

T1


T

T2

+

NT A

1 1


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Molecular Tectonics

T1 and T2 Non-Interconvertible Tectons

Atoms

Interatomic Link by

Covalent Bond (Non reversible)

Molecular Synthesis

Tecton (T1) Tecton (T2)

Supramolecular Synthesis Intertecton Link byNon-Covalent Bond (revresible)




T1

T2

N

T1 A

1 1

NT2 A

1 1

Networks

Same Topology (1-D) but Different Geometry

Conservation ofConfigurationInvariance ofinteratomic

Connectivity


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Molecular Networks

Nd

TiTjTk

n

Ai

d = 1, 2 or 3 n = i+j+k = or > 1Dimension

Tectons

Number of Tectons

Number of AssemblingCore Ai = or > 1

NT1T2 A1

T1

T2A1

1 2

NT1T2 A1

T1

T2

A12 2

T1

T2

NT1T2 A1

3 2


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1-D Molecular Networks

Nd

TiTjTk

n

Ai

d = 1, 2 or 3 n = i+j+k = or > 1

Dimension

Tectons

Number of Tectons

Number of Assembling Core

Ai = or > 1

N1

T1

1

A1

T1 A1

N1

T1T2

2

A1T1 T2 A1

T1= Self-complementary

T1and T2 = Complementary

N1

T1T2

2

A1A2

T1 T2 A1 A2

T1 T2 T3

N1

T1T2T3

3

A1A2A3

A1 A2 A3

T1, T2 and T3 = Complementary


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2-D Molecular Networks

N2

T1

1

A1

A1

T1

T1= Self-complementary

N2 1

A1T1

T1

N2 1

T1

A1

A2

T1

T1

T2N2 2

A1T1T2

A1

T1and T2 = Complementary

N2 2

T1T2

A1

A2

T1

T2

A1A2

N2 2

A1A2T1T2

T1

T2 A1

A2


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Molecular Tectonics: self-assembly of Programmed Tectons

Analysis Design

Assembling Nodes

Self-reparation : Reversible assembling

C

A B

Low activation barriers (Ea) : self-healingprocess. Many different intermediate statesbut one final state.

E

Ea

E


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Reversibility and Self-healing

Final state

Initial state

Intermediate state

A

B

C

High activation energies (Ea) : non-healing process. Coexistence ofmany different final states.

C

Low activation barriers (Ea) : self-healingprocess. Many different intermediatestates butonefinal state.

A B

CB

G = 0 between state B and C, low activationEnergy (Ea) between B and C: coexistence of twointerconverting polymorphes

E

G = 0

Ea

Ea

A E

E

E

Ea

E

Ea

E

CB

E

G

Ea

A E

Small G between states B and C, high activationEnergy (Ea) between B and C: coexistence of two non-interconverting polymorphes


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Packing of 1-D Molecular Networks

X

Y

Z

N1

T1T2

2

A1

Orientation of the Newtork along X

Free arrangement along Y and Z

T1

T2A1

Y

X

X

Y

X

X

ZZ

X

Y

Z


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M. W. Hosseini, Cryts. Eng. Comm., 2004, 6, 318.

Packing of 1-D Networks

NT1T2 A1

1 2

y

x

y

x

z

x

T2

T1

A1


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Packing of Molecular Networks

X

Y

Z

N2

T1T2

2

A1

Orientation of the Newtork alongX and Y.Free arrangement along Z

T1

T2

A1A1

Z

X

Y

Z

N3

T1T2

2

A1Orientation of the Newtork alongX, Y and Z

T1

T2

A1


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Rseaux Molculaires par Inclusion


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Inclusion Complex

Clathrate

Receptor Substrate

Endomolecular Cavity

Exomolecular Cavity

+

+

Clathrand

Koiland Koilate

Endomolecular CavityExomolecular Cavity

Inclusion Networks

F. HAJEK, M. W. HOSSEINI, E. GRAF, A. DE CIAN, J. FISCHER,Angew. Chem. Int. Natl. Ed. Engl. 1997, 36, 1760-1762.

Substrate

+

Connector

Solution

or Solid statee

Solid statee

Solution

or Solid statee


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Directional and non-directional koilates


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CALIXARENES

O

HHO

H

O

OH

R

RR

R

calixarene : n = 1 to 4

n

OH

OH

OH HO

R R

RR

OHOH

OH

OH

RR

R

Rcone

OH

OHOH

R RR

R

OH

OH

R R

RR

OH

RR

R

HO

OH

R

HOOH

1-2 alternate 1-3 alternate partial cone

OHOH

OH

OH

R

RR

R

OH

OHHO

OH

R

R

R

R

HO

OH

OH

OH

R

R

R

R

HO


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THIACALIX[4]ARENE,SULFONYLCALIX[4]ARENE ANDSULFINYLCALIX[4]ARENE

SS

SS

OH

HO

OH

OH

SOOS

SOOS

OH

HO

OH

OH

SO2O2S

SO2O2S

OMe

MeO

OMe

OMe

SO2O2S

SO2O2S

OH

HO

OH

OH


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Fused Calix[4]arenes

O

O

O

O

O

Si

O

OO

Si SiSi


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Fused Calix[4]arenes

TiTiOO

O

O

OTi

O

OO

Ti

M. M. Olmstead, G. Sigel, H. Hope, X. Xu, P. P. Power

J. Amer Chem. Soc. 1985, 107, 8087

AlAlO

OO

O

OAl

O

OO

Al

J. L. Atwood, S. G. Bott, C. Jones, C. L. Raston

J. Chem. Soc., Chem. Comm.,1992, 1349


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Towards Directional 1-D Inclusion Networks

OO

O

O

O

O

OO

[A,A,M,M]

Centrosymmetric

OOH

OH

O

O

OH

OHO

OO

O

O

O

O

OO

[A,A,M1,M2][A,A,M]

Electronic differentiation

O

OO

O

O

O

OO

O

OO

O

O

O

OO

[A,B,M,M] [A,B,M1,M2]

Electronic and geometricdifferentiation

Geometricdifferentiation

Non-centrosymmetric


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O

O

OO

O

OO

O

SiSi

O

O

O

OO

O

OO

O

SiSi

O

O

O

OO

O

OO

O

SiSi

O

O

O

OO

O

OO

O

SiSi

O

O

O

OO

O

OO

O

SiSi

O

O

O

OO

O

OO

O

SiSi

O

O

O

OO

O

OO

O

SiSi

O

O

O

OO

O

OO

O

SiSi

O

O

O

OO

O

OO

O

SiSi

O

O

OO

O

OO

SiSi

O

O

Combinatorial Library of Koilands

OH

HO

OHOH

OH

HO

OHOH

OH

HO

OHOH

OH

HO

OHOH

X. Delaigue, M. W. Hosseini, A. De Cian, J. Fischer, E. Leize, S. Kieffer, A. Van Dorsselaer,

Tetrahedron Lett. , 1993, 34, 3285-3288.

F. Hajek, E. Graf, M. W. Hosseini, X. Delaigue, A. De Cian, J. Fischer, Tetrahedron Lett., 1996, 37, 1401-1404.


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Discrete 2/1 Inclusion Complex

OO

O

OO

SiO

OO

Si


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Discrete 2/1 Inclusion Complex

OO

O

OO

SiO

OO

Si


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Inclusion Network

OO

O

OO

Si

O

OO

Si

F. Hajek, M. W. Hosseini, E. Graf, A. De Cian, J. Fischer,Angew. Chem. 1997, 36, 1760-1762.


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Directional Koilates

O

O

O

O

O

Si

OO

O

SiOH

HOOH

OH

OH

HOOH

OH


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Directional KoilatesUnsymmetrical Koiland & Symmetrical Connector

OOH

OH

O

O

OH

OHO

Si


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NC

NC

CN

CN

NN

NN

HH

HH

NN

NN

HH

HH

Rseaux Molculaires par Liaison Hydrogne


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H-Bonding

H-bond defined by:

Electronegativity of X and Y

Distance d between X and Y

XHY Angle

X H Y

d

Angular distribution : 120 <


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O

H

O

AAAA

AAAD

O2-

OH-

O

R

AAA

RO-

Eau Alcool Ether

Eau, Alcool et Ether

-H+

OH

H

O

H

H H

AADD

ADDD

H2O

H3O+

OR

H

O

R

H H

AAD

ADD

ROH

ROH2+

OR

R

O

R

R H

AA

AD

ROR

RO(H)R+

-H+

+H+

Eau Alcool Ether

O

H

H H

H

DDDD

H4O2+

O

R

H H

H

DDD

ROH32+

O

R

R H

H

DD

RO(HH)R2+

+H+

OH

H

AADD

H2O

O

R

H

AAD

ROH

OR

R

AA

ROR

-H+

Dprotonation (caractre acide) Protonation (caractre basique)


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N

H

H

N

H

H H

AADD

ADDD

NH2-

NH3

N

R

H

N

R

H H

AAD

ADD

RNH-

RNH2

N

R

R

N

R

R H

AA

AD

R2N-

R2NH

N

R

R R

A

R3N

Amine, Amidate and Ammonium

Amine

Amidate-H+

+H+

NH

H H

H

DDDD

NH4+

NR

H H

H

DDD

RNH3+

NR

R H

H

DD

R2NH2+

NR

R R

H

D

R3NH+

Ammonium


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D-H

ADonor

Acceptor

D-H

dDA (Distance) et DHA (Angle)Monohapto Mode of interaction

A

D-H

A

HD

A

Double Donor

Double Acceptor

D-HHD A A

Discrete Entity

1-D Network

Monohapto Mode of interaction

D-HHD

D-HHD

A A

A A

A A

A A

D-HHD

D-HHD

1-D Network

Dihapto Mode of interaction

Design of H-Bonded Networks

Quadruple Acceptor

Quadruple Donor

M. W. Hosseini, Coord.Chem. Rev., 2003, 240, 157.


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H

H

H

H

O

O

O

O

H

H

H

H

O

O

O

O

H

H

H

H

O

O

O

O

Dicationic Tecton T2+ Dianionic Tecton T2-

Simultaneous use of H-Bond and Electrostatic Interactions

H-Bond : Weak but Directional

Charge/Charge Interactions : Strong but less Directional

Tetra H-bond Donor (DDDD) Tetra H-bond Acceptor (AAAA)

Dihapto Mode of H-Bonding

NT1T2 A1

1 2


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H

H

H

H

Dicationic Tecton T2+

Dicationic H-Bond Donor Tectons : Bisamidinium

Tetra H-bond Donor (DDDD)

N

N

N

N

H

H H

N

N

H

H

N

N

H

H

H+

N

N

H

N

N

H

N

N

H

H

N

N

H

H

2H+

N

N

H

H

N

N

H

H

d

Spacer

Spacer


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(CH 2)nN

NN

N

H H

HH

N

N

(CH2)nN

N

HH

HH

N

NN

N

H

H

H

H

N

NN

N

HH

HH

(CH 2)2N

NN

N

H H

HH

OHHO

N H

HNNHH

H N

H

H

H

H

N

NN

N

H

H

H

H

N

N

N

NH

H

HH

N

NN

N

HH

HH

N

NN

N

H

H

H

HN

N

N

N

HH

H H

N

NN

N

H

H

H

H

N

NN

N

H

H

H

H

S S

SS

NN

HH

HH

N

N

H

H

H

H

N

N

H

H

H

H

(CH 2)2N

NN

N

H H

HH

(CH 2)2

N

NN

N

H H

HH

Amidinium Polycations

n = 1,2,3,4 n = 1,2,3,4

Dicationic Tectons for H-Bonded Networks

R

R

R

R

C6, C12, C18 C6, C12, C18

O. Flix, O.; Hosseini, A. De Cian, J. Fischer, Chem. Comm., 2000, 281-282.

O. Flix, M. W. Hosseini, A. De Cian, J. Fischer,New J. Chem., 1998, 22, 1389-1393.

G. Brand, M. W. Hosseini, R. Ruppert, A. De Cian, J. Fischer, N. Kyritsakas,New J. Chem., 1995, 19, 9-13.


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NH

NH

HN

HN

CO2

CO2O2C

O

O

NN

N N

H

H

H

H

O

O

O

O

O

O

NN

N N

H

H

H

H

O

O

O

O

NN

N N

H

H

H

H

From discrete binuclear complex to 1-D Network

O. Flix, M. W. Hosseini, A. De Cian, J. Fischer, Tetrahedron Lett., 1997, 38, 1755-1758.

Discrete

1-D Network


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CO2HHO2CNH

HN

NH

HN

2-D H-Bonded Molecular Network


52/138


NH

HN

NH

HN

HO2C CO2H


53/138

NH

HN

NH

HN

CO2H

CO2H

1-D H-Bonded Network


54/138


T2

T1

A1

N

T1T2 A1

1 2

NH2

NH

HN

H2N

A1

CO2O2C

T2

O2C

CO2

M. W. Hosseini, R. Ruppert, P. Schaeffer, A. De Cian, N. Kyritsakas, J. Fischer, Chem. Comm., 1994, 2135-2136.

O. Flix, M. W. Hosseini, A. De Cian, J. Fischer,N. J. Chem., 1998, 22, 1389-1393.


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Formation of -NetworksN

H

HN

NH

HN

CO2O2C- -

N


56/138

Formation of -Networks

NH

HN

N

H

HN

NO2

CO2O2C- -


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C C NN

C C NN

C

N

C

N

MII

II

M(CN)2-

M(CN)42-

M

C C NN

C

N

C

N

C

N

C

N

II

M(CN)64-

M C C NN

C

N

C

N

C

N

C

N

MIII

M(CN)63-

Polycyanometallate complex anions


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M(CN)2-

1-D H-Bonded Networks

NN

NN

HH

HH

O

O

O

O

NN

NN

HH

HH

NC

CNNC

CN

NN

NN

HH

HH

NN

NN

HH

HH

NC

NC

CN

CN

NN

NN

HH

HH

NN

NN

HH

HH

a)

b)

c)

M(CN)42-

Dicarboxylates

Dihapto

Dihapto

Bis Monohapto

Modulation of M ....M Distance


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-200

0

200

400

600

800

1000

1200

250 300 350 400 450 500 550

[Au(CN)2]2[C

8H

16N

4]

U

A

/ nm

M(CN)2-

5.0 1-D H-Bonded Networks

NC

NC

CN

CN

NN

NN

HH

HH

NN

NN

HH

HH

N

N

N

N

H

H

H

H

3.3

Aurophilic Interactions

C. Paraschiv, S. Ferlay, M. W. Hosseini, V. Bulach, J.-M. Planeix, Chem. Comm., 2004, 2270.


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3.333

N

NN

N

H

H

H

H1-2H+

H H

H H

H H

H H

M CNNC2-

NT1T2 A1

1 2

1-D Hybrid H-Bonded Networks

Au

M = Au M = Ag

3.377

Ag

4.224

Au

4.048

N

N N

NH

H

H

H2-2H+

Ag

C. Paraschiv, S. Ferlay, M. W. Hosseini, V. Bulach, J.-M. Planeix, Chem. Comm., 2004, 2270.


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Pd(CN)42- Pt(CN)4

2-Ni(CN)42-

1-D Hybrid H-Bonded Networks

N

NN

N

HH

HH

7.0

4.4

First Coordination Sphere

NiC NH Pd Pt

SecondCoordination

Sphere

S. Ferlay, V. Bulach, O. Flix, M. W. Hosseini, J.-M. Planeix, N. Kyritsakas, Cryst. Eng. Comm, 2002, 4, 447.


65/138

Supramolecular Chirality

Molecular Chirality of the and Type

First Coordination Sphere Second Coordination Sphere

''

Supramolecular Chirality of the ' and ' Type

S. Ferlay, M. W. Hosseini, Chem. Comm., 2004, 788.


66/138

N

NN

N

HH

HH

Cr(CN)63-

4.4 7.0

Porous 2-D H-Bonded Networks

C

N

H

Cr

O ' and ' Chirality


67/138

N

NN

N

HH

HH

Porous Isostructural H-Bonded Networks

Fe(CN)63-

4.4 7.0

Cr(CN)63-

Co(CN)63-

S. Ferlay, M. W. Hosseini, Chem. Comm., 2004, 788.



68/138

MM

ML4YZML5Z

Achiral

Supramolecular Chirality

MM

Chiral

' '

ML4YZ

Achiral

Chelating unit

S. Ferlay, R. Holakovski, M. W. Hosseini, J.-M. Planeix, N. Kyritsakas, Chem. Comm, 2003, 1224-1225.


69/138

HN

HNNH

NH

Achiral tecton

Chiral and Achiral H-Bond Donor dicationic tectons

NH2

NH2

R

R

*

*

(R,R)

HN

N

H

R

R

*

*

HN

N

H

R

R

*

*

(R,R,R,R)

H2N

H2N

*

*

S

S

(S,S)

HN

NH

*

*

HN

NH

*

*

S

S

S

S

(S,S,S,S)Chiral tectons

NH2

NH2



70/138

Chiral Charge Assisted H-Bonded Networks

HN

NH

HN

NH

HN

NH

HN

NH

S

S

S

S

N

NN

N

HH

HH

Fe(II)

CN

NO

R

R

R

R

[Fe(CN)5NO]2-

Achiral Chiral' '

N

NN

N

HH

HH

C N O Fe

'

'

HN

NH

HN

NH

R

R

R

R

HN

NH

HN

NH

S

S

S

S



71/138

S. Ferlay, M. W. Hosseini, Chem. Commun., 2004, 788-789

NT1TFe A1

NT1TFe A1

H2

2

TFeTRu TRuTFe

TFeTRuTFe TRuTFeTRu

NT1T2 A1

2 H Fe(CN)64-

4.4

Ru(CN)64-TRu

TFe

N

NN

N

HH

HH

7.0

T1

NTFe A1

H2N A1

2NT1TRu A1

2

NT1TCo A1

H2Generation 0

Generation I

Generation II

Crystals of Crystals

T1TRu

H

HH


72/138


Ru(CN)64- Fe(CN)6

4-

Ru

C

N

H

Fe

N

NN

N

HH

HH

7.0

M(CN)64-

4.4

Two almost identical crystallin systems (isomorphic and isometric)


73/138

NT1TFe A1

2 H

TRuTFe

NT1T2 A1

2 H Fe(CN)64-

4.4

Ru(CN)64-TRu

TFe

N

NN

N

HH

HH

7.0

T1

NTRU A1

H2N

A1

2 H

Generation 0

Generation I

Composite Crystalls

T1TFe


74/138

Cristaux Gigognes

Fe(CN)64- + Ru(CN) 6

4- Fe(CN) 64-Ru(CN)6

4-

N

NN

N

HH

HH

7.0 4.4

GI GI

GII

GIII GIV


75/138


76/138


77/138

Rseaux Molculaires par Liaison de Coordination


78/138

. . .. . .

metal

. . . . . .

S

S

S

S

. . .. . .

. . . . . .

S

S

S

S

Coordinating polymer

organic connector

metal

Coordination polymer


79/138

Why Coordination Networks ?

Because transition metals offer numerous oxidation states, coordination geometry as well asphotochemical and magnetic properties, the design and preparation of coordination polymers (which maybe regarded as metallo-organic networks) may be an important area of research in material science.One may design coordination polymers by mathching the coordination demandes of the linking metal withthose of the bridging organic ligand.

400400 500 600600 700 800800 900

0.0

0.5

1.0

1.5

2.0

A

nm

600600 700 800800

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

A

nm

Photochemistry

-20

-15

-10

-5

0

5

10

15

20

00.20.40.60.81

Reversibility of Copper II complexe

50100200300400600

V

mV/s

REDOX Chemistry

0

0.1

0.2

0.3

0.4

0.5

0 50 100 150 200 250 300

m

T (emu mol-1

K)

T (K)

Magneto Chemistry

MetallicTecton

Coordination Geometry


80/138

Design of Coordination Networks

Backbone

Pole CP 2

Pole CP 3Pole CP 1

A, B, C = Coordination sitesn, m, o = number sites (denticity)

CP = Coordination Polesx = number of poles

Exoligand = Tecton : Lx (nA,mB)

M

Metal = Tecton : My (CG,NS,CPi,OS)

y = coordination numberCG = Coordination GeometryNS = Number of Coordination site availableCPi = Coordination poleOS = Oxidation State

OrganicTecton

MetallicTecton

Ln-(Anionic) Mn+

(Ln- Mn+)

OrganicTecton MetallicTecton

L (Neutral) Mn+

(LMn+ An-)Anion

An-


81/138

Endo-ligand Endo-molecular complex

Exo-ligand

Exo-polynuclear complex Coordinationpolymer

Discrete Exo-binuclear complex

Molecular Networks Based on Coordination bond


82/138

Design of exo-ligands

Backbone

Pole CP 2

Pole CP 3Pole CP 1

Exoligand : Lx (nA,mB)

A, B, C = Coordinating sitesn, m, o = number sites (denticity)

CP = Coordination Polesx = number of poles

LII (1A,1B) LII (1A,1A) LII (2AB,1C) LII (2AA,1B) LII (2AA,1A)

LII (2AB,2CD) LII (2AA,2AA)LII (2AA,2BB)

LII (3ABC,1D) LII (3ABC,1D) LII (3AAA,1B)

LII (3ABC,3DEF) LII (3AAA,3BBB) LII (3AAA,3AAA)


83/138

Site Protection & Topological Changes

Free Site (Labile Ligand) Protected Site (Strongly Coordinating Ligand)Metal Centre

120

120

90

180

107

90

180

9090

90


84/138

Site Protection & Topological Changes

Free Site (Labile Ligand) Protected Site (Strongly Coordinating Ligand)Metal Centre

90 90

90

180909090

90180

90

9090


85/138

Design of 1-D Coordination Networks

+

+

+

+

+

+

+

Bis-Monodentate

Bis-Bidentate

Bis-Tridentate


86/138

1-D Network : Geometry

a) b)

c)d)

Linear Stair

Zig-Zag

Helical

Sil C ti


87/138

Ag

Ag Ag

ReversibleL + Ag+ [LnAg]+

Ag

Loose Coordination requirelents

Linear

Trigonal T type

Tetrahedral

3 coordination sites



Ag Ag

Metal-Metal interactions

Peculiar interaction mode

Ag

Cation- interactions

Silver Cation


88/138


89/138

Coordination Polymers

N N

(CH2)n

(CH2)m

4 n = m = 05 n = 0, m = 16 n = 2, m = 2

CNNC

N N CNNC N N CNNC


90/138

N N N C N

O O

FF

F

FF

F

Labile ligands

Neutral Complex

Monoanionic chelates

Directional 1-D Coordination Networks

Cu

V. Jullien, PhD Thesis, ULP, 2002.


91/138

O

NN

O

O

N

O

N

O O

N

O

NN

O

O O

N

1

2

Coordinating site

Modulable spacerMacrocyclic backbone

1-D Coordination network

Cu(OAc)2

E. GRAF, M. W. HOSSEINI, J.-M. PLANEIX, N. KYRITSAKAS,New J. Chem, 2005,29, 343-346.

2-D Silver Coordination networks


92/138

N N

N

N

PF6

-AsF6

-

SbF6-

BF4-

2 D Silver Coordination networks

D. POCIC, J.-M. PLANEIX, N. KYRITSAKS, A. JOUAITI, M. W. HOSSEINI, Cryst. Eng. Comm., 2005, 7, 624-628.


93/138

Fluorene based Tectons

OO

NN

O O

OO

NN

O O

OONN

O O

OO

NN O O


94/138

Organi [1,1] Tecton

T1T2

HgCl2

Metallatecton

Fluorene based Tectons and Coordination Networks

OO

NN

O O

N1

T1T2

2

A1

A1

1-D Coordination Network

Packing


95/138

Tubular Coordination Network


96/138

C. Klein, E. Graf, M. W. Hosseini, A. De Cian, J. Fischer, Chem. Comm., 2000, 239-240.

Organic Tecton

M

Tubular Coordination Network

Metallatunulane

S4 Axis


97/138

Design of ex-ligand based on meta[1 1 1 1]cyclophane


98/138

Design of ex ligand based on meta[1,1,1,1]cyclophane

X

X

X

X

1 X = OH2 X = Br3 X = CN

7.78

The 1,3-alternate blocked conformation

NC

CN

CN

CN

7.90

Metallatubular Molecular Networks


99/138

Metallatubular Molecular Networks

NC

CN

CN

CN

C. Klein, E. Graf, M. W. Hosseini, A. De Cian, J. Fischer, Chem. Comm., 2000, 239-240.


100/138

O

O

O

O N

N

N

N

O

O

O

O

Molecular tectonics: on the formation of tubular coordination networks

G. Laugel, E. Graf, M. W. Hosseini, J.-M. Planeix, N. Kyritsakas,New J. Chem., 2006,30, 1340 -1346


101/138


102/138

Double stranded helical coordination networks


103/138

A. Jouaiti, M. W. Hosseini, N. Kyritsakas, Chem. Comm, 2003, 473-474.

Tuning the Pitch

O O O O O

NN

O O

O O O O O OO

N

OO

N

Single strand Double strandHomochiral

Packing of Double strands

Formation of a Racemate


104/138

J. Bourlier, M. W. Hosseini, J.-M. Planeix, N. Kyritsakas, New J. Chem, 2006, ASAP

O O

O O

CNNC

O

O O O

CNNC

O

O O O O

CNNC

O

O O O O O

CNNC

O CNNC

R

OCN

R

OCN

Increased coordination propensity

O O CNNCO

Primary Secondary

Combination of primary and secondary coordination poles

1-D Helical Silver Coordination Networks


105/138


1 D Helical Silver Coordination Networks

O O O O O O O OCNNC O CNNC

Doubly interdigitated heliceswith Opposite handedness

Helical network

2-D Interwoven Silver Coordination Networks


106/138


2 D Interwoven Silver Coordination Networks

Interwoven helical Strands

with same handedness

Helical network

O O O O O O CNNC

Chiral Tectons


107/138

Chiral Tectons

O

O

HH

OH

HO

O

O

HH

OH

HO

Isomannide Isosorbide

Enantiomerically pure scaffolds

O

OHH

O

O

O

N

O

N

O

OHH

O

O

O

N

O

N

O

O

HH

O

O

O NON

O

O

HH

O

O

O NON

1

2

3

4Bis-monodentate

C N O

O

OHH

O

HO

O

N O

OHH

O

HO

O

N

5 6

H-Bonding Tectons

H-bond Donor/Acceptor

Coordinating Tectons

From enantiomerically pure sugars to enantiomerically


108/138

y p g y

pure helical coordination network

O

O

HH

O

O

O

N

O

N

O

O

HH

OH

HO

Isomannide

N

1

T1T2

2

A1

*

T1*

Chiral

HgCl2

T2 Achiral

Crystal system : Monoclinic

Space group : C2

a () : 30.25

b () : 7.49

c () : 8.79

(deg) : 92.36V (3) : 1989.57

Z : 4R : 0.039

Cl

Hg

Cl

N N

A1

Single stranded Helix

P. Grosshans, A. Jouaiti, V. Bulach, J.-M. Planeix, M. W. Hosseini, J.-F. Nicoud, C. R. Chimie.2004, 7, 189-196.

Single Helical Coordination nEtworks


109/138

PM

g

Possible Packing

P. GROSSHANS, A. JOUAITI, V. BULACH, J.-M. PLANEIX, M. W. HOSSEINI, J.-F. NICOUD, C. R. Chimie.,

2004, 7, 189-196.

From enantiomerically pure sugars to enantiomerically


110/138

pure triple stranded helical coordination network

O

O

HH

OH

HO

O

O

HH

OH

HO

Isomannide Isosorbide

O

O

HH

O

O

O

N

O

N

O

O

HH

O

O

O

N

O

N

HgCl2

Triple stranded Helix

P. Grosshans, A. Jouaiti, V. Bulach, J.-M. Planeix, M. W. Hosseini, J.-F. Nicoud, Chem. Comm, 2003, 1336-1337.

Possible Packing of rods


111/138

Hexagonal (honeycomb) Packing Tetragonal Packing

M. OKeeffe, S. Andersson, Acta Cryst., 1977, A33, 914

Orthogonal packing of enantiomerically pure helical silver coordination networks


112/138

A. Jouaiti, M. W. Hosseini, N. Kyritsakas, P. Grosshans and J.-M.Planeix, Chem. Commun., 2006, 3078-3080

O

O

Br

Br

N

N

O

O

rare cubic space group (I213)

Orthogonal packing of enantiomerically pure helical silver coordination networks

Bi idi th t d Ch l t


113/138

N

N

N

N N

N

N

N

N

N

N

N

3,3'4,4'

2,3'2,4'

3,4'

2,2'

5

5'

Bipyridine: the most used Chelate

N

N N

N N

N N

N

N

N

N

N

N

N

N

N

6

6'

2

2'

2

2'

4

4'

2

2'

5

5'

Endo-Ligands Exo-Ligands

2

2'

5

5'

C. Kaes, A. Katz, M. W. Hosseini, Chem. Rev., 2000, 100, 3553-3590.


114/138

C. Kaes, M. W. Hosseini, C. E. F. Rickard, B. W. Skelton, A.H. White, Angew. Chem. Int. Natl. Ed. Engl.

1998, 37, 920-922.

Packing of Directional and Non-directional 1-D Networks


115/138

+

+ Or + Or

+ +

AchiralCentric

Centre of Symmetry

Non-Directional

Apolar

Apolar

Directional

Non-Directional

Apolar Polar

Anti// Syn //

Polar

Anti// Syn //Directional

Non-Directional

Apolar Apolar

Or

Apolar

Anti// Syn // Syn //Anti//

Apolar

Or

AchiralAcentric

C2 Chiral

C2 ChiralAchiralAcentric

D i f Di ti l C di ti N t k


116/138

Design of Directional Coordination Networks

Tridentate Monodentate

Coordinating Tecton

Monoanionic ligands

Labile ligands

Neutral Complex

Directional 1-D Coordination Network

Non Centrosymmetric PackingCentrosymmetric Packing

Directional 1-D Coordination Networks


117/138

N N

N

N

trihapto monohaptoMonoanionic ligands

Labile ligands

Neutral ComplexCoCl2

Co

Cl

2.46

2.13

2.16

2.05

Centrosymmetrical Packing

A. Jouaiti, M. W. Hosseini, A. De Cian, Chem. Comm., 2000, 1863-1864.

Polar Crystals


118/138

N N

N

O

O

N CoCl2

Acentric Packing

MOh(t,4)

T(1,3)

AchiralMetallatecton

C2-Chiral [3,1]-Tecton

A. Jouaiti, M. W. Hosseini, N. Kyritsakas, Chem. Comm, 2002, 1898-1899.

Packing of Directional 1-D Networks


119/138

x

Syn

y

Anti //Syn //

z

Anti

y

Anti

Anti //

z

+N

T1T2 A1

1 2

T1 T2

Apolar

Apolar

ApolarPolarPolar

Directional 1-D Network


120/138


121/138

Characterisation by X-Ray Crystallography

N

S

S

Cd

Cl

N

S

S

Cl

Cl

Cd

Cl

S

S

S

S

N Cl

N Cl

Cd

Cl

Cl

Cl

CdCl

Characterisation by X-Ray Crystallography


122/138

Characterisation by X Ray Crystallography

N

S

S

Cd

N

S

S

Cl

Cl

Cd

Cl

N

S

Cd

N

S

S

Cl

Cl

Cd

Cl

S

S

S

S

S

S

S

S

N

N Cl

Cl

N

N Cl

Cd

Cl

Cl

Cd

Cl

Cl

Cl

Cl

Cl

Cd

CdCl

Cl S

N

S

S

Cd

Cl

N

S

S

Cl

Cl

Cd

Cl

S

S

S

S

N Cl

N Cl

Cd

Cl

Cl

Cl

CdCl

Gradual increase in connectivity


123/138

Gradual increase in connectivity

M

M

M

MN

T1T2 A1

1 2 M

M

M

MM NT1T2 A1

2 2

MM

Coordination site

Coordinating site

Organic tectons

Metalla tectons

M

M

MM NT1T2 A1

2 2

MM

M

MM

M

M

M

NT1T2 A1

3 2

From 1-D to 2-D NetworksM M


124/138

O

O

O

O

N

N

N

N

O

O

O

O

M M

M MMonodentate monoanion

Available coordination site

C N O CoClC N O HgCl

C2v

D4h

D4h

From 1-D to 2-D Networks


125/138

+

Recognition patterns

N

2

T1T2

2

A1A2

T1 T2

N

2

T1T2

2

A1

N

2

T1T2

2

A2A1A

2

J. PANSANEL, A. JOUAITI, S. FERLAY, M. W. HOSSEINI, J.-M. PLANEIX, N. KYRITSAKAS

New J. Chem., 2006,1, 71 - 76

From 1-D to 2-D Networks

O


126/138


New J. Chem., 2006,1, 71 - 76.

C N O HgCl

O HgClN

d)

Assembling NodesN-M-N

O-M-O

NN

H

N

NO

Trans Trans

H

Anti //

From 1-D to 2-D Networks NNO

O

H

HNN

O

O

H

H

NNOH

NNOH


127/138


New J. Chem., 2006,1, 71 - 76.

C N O HgCl

NN

H H

NN

O ONN

O HNN

O H

NNO

O

H

HNN

O

O

H

H

N Cl Hg

Assembling nodesCoordination bond

Hydrogen bond

i i C i i N


128/138

3-D Diammonoid Coordination Networks

M

M

M

M

M

M

M

L

L

L

L

L

L

L

L

L

LL

M

M

M

L

M

Td Linear

L

b)

M

M

M

M

MM

M

M

M

MMM

L

L

L

L

L

L L

L

L

L

L

Td

M

Linear

M

L

M

M

M

M

M

L

L

L

M

Td

L

Td

3-D Coordination Networks


129/138

N

N

N

N

M

M

M

M

MM

M

M

M

MMM

L M

L

L

L

L

L

L L

L

L

L

Td Linear

Ag

dAg-Ag = 3.08

NAgN = 178.4

3-D diamondoid Coordination Network

3-D Coordination Networks


130/138

N

N

N

N

M

M

M

M

MM

M

M

M

MMM

L M

L

L

L

L

L

L L

L

L

L

Td Linear

Four-fold homo interpenetration

dAg-Ag = 3.08 NAgN = 178.4

Design of Tectons for Construction of 3-DCoordination Networks


131/138

M

L

M

M

M

M

ML

L

L

M

L

Td

TdOH

CN

NC

CN

H

CN

NC

CN

Design of 3-D Coordination Networks


132/138

M

L

M

M

M

M

M

L

L

L

M

L

Td

Td OH

CN

NC

CNAg

N

CO

Diamandoid 3-D Network

Two-Fold Homo interpenetration

D i f 3 D C di ti N t k


133/138

Design of 3-D Coordination NetworksM

L

M

M

M

M

M

L

L

L

M

L

Td

Td

OH

CN

NC

CN

Diamandoid 3-D Network Two-Fold Homo interpenetration Porous Network : inclusion of solvents

Porphyrin as a skeleton for the design of tectons


134/138

NH N

HNN

N N

NN

Porphyrin Metallaporphyrin

N N

NN

Meso-substitution

N N

NN

-Pyrr-substitution

NH N

HNN

Meso-substitution

NH N

HNN

-Pyrr-substitution

N N

NN

Mesoand -Pyrr-substitution

NH N

HNN

Mesoand -Pyrr-substitution

Robust Porous Crystals


135/138

E. Deiters, V. Bulach, M. W. Hosseini, Chem. Comm. 2005, 3906 - 3908.

+

ComplexationLigand Self-complemenrary

Tecton

Metal

Self-complemenraryTecton

Self-assembly

NNH

N HN

NN Zn2+NN

N N

NN

Neutral TectonLigand

Porous 3-D Coordination Network



136/138

+

ComplexationLigand Self-complemenraryTecton

Metal

NNH

N HN

NN Zn2+NN

N N

NN


dZn-Zn = 10.038 dZn-Zn = 10.006 dZn-Zn = 10.037 dZn-Zn = 10.056

a = 32.9114(13) b = 32.9114(13) c = 9.4246(5) Volume8840.7(7) 3

a = 33.0866(4) b = 33.0866(4) c = 9.4360(2) Volume8945.9(2) 3

C. S. RhombohedralSpace group R-3Z = 9

a = 33.0583(7) b = 33.0583(7) c = 9.3302(5) Volume8830.4(5) 3

a = 33.0734(5) b = 33.0734(5) c = 9.2921(4)

Volume8802.4(4) 3

Single-Crystal-to-Single -Crystal Transformation


137/138

E. Deiters, V. Bulach, M. W. Hosseini, Chem. Comm. 2005, 3906 - 3908.

VacuumEtOH

Cyclohexane

MeOHVapor

MeOH

CyclohexaneLiquid Vacuum

a) b)

c)d)

EtOHVapor

CyclohexaneLiquid

Vacuum

CyclohexaneLiquid

Robust Porous CrystalsF F


138/138

+

Ligand Self-complemenraryTecton

Metal


NNH

N HNNN Zn2+

NN

N NNN


F

F

F

F

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Autoassemblage Hosseini