autoassemblage hosseini
TRANSCRIPT
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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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Rfrences Bibliographiques
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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Rfrences Bibliographiques
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)
Complementaryinteraction sites
Tecton (T)
Self-Complementary Tecton
Supramolecular Synthesis Conservation of ConfigurationNon-Covalent BondIntertecton Link (A)
Networks
Complementary Tectons
NT1T2 A
1 2
T1
Self-Complementary Tecton
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)
Complementaryinteraction sites
Self-Complementary Tecton
Self-Complementary Tecton
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
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1-D H-Bonded Molecular Network
NH
HN
NH
HN
HO2C CO2H
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NH
HN
NH
HN
CO2H
CO2H
1-D H-Bonded Network
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1-D H-Bonded Molecular Network
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
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Formation of -Networks
NH
HN
N
H
HN
NO2
CO2O2C- -
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-
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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.
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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.
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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
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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.
S. Ferlay, V. Bulach, O. Flix, M. W. Hosseini, J.-M. Planeix, N. Kyritsakas, Cryst. Eng. Comm, 2002, 4, 447.
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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.
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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
S. Ferlay, R. Holakovski, M. W. Hosseini, J.-M. Planeix, N. Kyritsakas, Chem. Comm, 2003, 1224-1225.
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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
S. Ferlay, R. Holakovski, M. W. Hosseini, J.-M. Planeix, N. Kyritsakas, Chem. Comm, 2003, 1224-1225.
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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
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S. Ferlay, V. Bulach, O. Flix, M. W. Hosseini, J.-M. Planeix, N. Kyritsakas, Cryst. Eng. Comm, 2002, 4, 447.
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)
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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
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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
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Rseaux Molculaires par Liaison de Coordination
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. . .. . .
metal
. . . . . .
S
S
S
S
. . .. . .
. . . . . .
S
S
S
S
Coordinating polymer
organic connector
metal
Coordination polymer
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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
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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-
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Endo-ligand Endo-molecular complex
Exo-ligand
Exo-polynuclear complex Coordinationpolymer
Discrete Exo-binuclear complex
Molecular Networks Based on Coordination bond
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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)
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Site Protection & Topological Changes
Free Site (Labile Ligand) Protected Site (Strongly Coordinating Ligand)Metal Centre
120
120
90
180
107
90
180
9090
90
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Site Protection & Topological Changes
Free Site (Labile Ligand) Protected Site (Strongly Coordinating Ligand)Metal Centre
90 90
90
180909090
90180
90
9090
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Design of 1-D Coordination Networks
+
+
+
+
+
+
+
Bis-Monodentate
Bis-Bidentate
Bis-Tridentate
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1-D Network : Geometry
a) b)
c)d)
Linear Stair
Zig-Zag
Helical
Sil C ti
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Ag
Ag Ag
ReversibleL + Ag+ [LnAg]+
Ag
Loose Coordination requirelents
Linear
Trigonal T type
Tetrahedral
3 coordination sites
2 coordination sites
4 coordination sites
Ag Ag
Metal-Metal interactions
Peculiar interaction mode
Ag
Cation- interactions
Silver Cation
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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
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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.
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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
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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.
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Fluorene based Tectons
OO
NN
O O
OO
NN
O O
OONN
O O
OO
NN O O
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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
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Tubular Coordination Network
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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
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Design of ex-ligand based on meta[1 1 1 1]cyclophane
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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
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Metallatubular Molecular Networks
NC
CN
CN
CN
C. Klein, E. Graf, M. W. Hosseini, A. De Cian, J. Fischer, Chem. Comm., 2000, 239-240.
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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
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-
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Double stranded helical coordination networks
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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
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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
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J. Bourlier, M. W. Hosseini, J.-M. Planeix, N. Kyritsakas, New J. Chem, 2006, ASAP
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
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J. Bourlier, M. W. Hosseini, J.-M. Planeix, N. Kyritsakas, New J. Chem, 2006, ASAP
2 D Interwoven Silver Coordination Networks
Interwoven helical Strands
with same handedness
Helical network
O O O O O O CNNC
Chiral Tectons
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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
-
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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
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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
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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
-
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Hexagonal (honeycomb) Packing Tetragonal Packing
M. OKeeffe, S. Andersson, Acta Cryst., 1977, A33, 914
Orthogonal packing of enantiomerically pure helical silver coordination networks
-
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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
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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.
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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
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+
+ 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
-
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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
-
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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
-
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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
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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
-
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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
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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
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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
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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
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+
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
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J. PANSANEL, A. JOUAITI, S. FERLAY, M. W. HOSSEINI, J.-M. PLANEIX, N. KYRITSAKAS
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
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J. PANSANEL, A. JOUAITI, S. FERLAY, M. W. HOSSEINI, J.-M. PLANEIX, N. KYRITSAKAS
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
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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
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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
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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
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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
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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
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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
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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
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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
Robust Porous Crystals
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+
ComplexationLigand Self-complemenraryTecton
Metal
NNH
N HN
NN Zn2+NN
N N
NN
Neutral TectonLigand
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
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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
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+
Ligand Self-complemenraryTecton
Metal
Robust Porous Crystals
NNH
N HNNN Zn2+
NN
N NNN
Neutral TectonLigand
F
F
F
F