1.1 Introduction

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Basis of Supramolecular Chemistry and Crystal
Engineering
1.1 Introduction Yesterday, Today and
Tomorrow 1.2 Intermolecular Forces 1.3 Basic
Concepts of Supramolecular Chemistry 1.4
Hydrogen-bonding in Crystal Engineering 1.5
Crystal Engineering of Coordination Polymers
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1.5 Crystal Engineering of Coordination Polymers

1. Important basis of coordination polymers and
   supramolecules
2. 0-D Supramolecules
3. Structural control supramolecular isomerism in
   low-dimensions
4. 1D-3D coordination polymers

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Frameworks ??
Inorganic Zeolites
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O.M. Yaghi, Science, 2002, 295, 469
Systematic Design of Pore Size and Functionality
in Cubic-like MOFs and Their Application in
Methane Storage
X-ray structures of the MOFs. Zn (blue
polyhedra), O (red spheres), C (black spheres).
The large yellow spheres the cavities
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desolvation
decomposition
Thermal stable up to 400 oC
Large capacity 800-1500 mg/g
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Zeolitic Metal-Organic Frameworks
M
?????

1

????? Zeolite nets
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135?-145 ?
In zeolites
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Zn(mim)2n?xsolvent-SOD Zeolite
(??)?????????d10??????????
Feature Small windows Large cavity
Topologic net
solvent accessible area 47.0
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Zn(eim)2n?xsolvent-RHO Zeolite
void 55.4
9
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Isotherm for N2 adsorption at 77 K (a) and MeOH
vapor adsorption at 298 K (b)
Zn(mim)2n-??SOD
Angew. Chem. Int. Ed. 2006, 45, 1557
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Thermal Stability
Zn(mim)2n- Zeolite SOD
Zn(eim)2n- Zeolite ANA
TGAgt450 ?C
TGAgt400 ?C
Thermogravimetric Analysis
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AgCl Hatz
Ag6Cl(atz)4(OH)6H2O8 (8)
NH3H2O
AgCl Ag2O Hatz
3-connected 4.142 net or 4-connected diamond net
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Ag
Cl
AgCl 3.060 Å
8.5 Å
5-fold interpenetration
Void 32.7
Tetragonal I _at_ 293K (8)
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Ag6Cl(atz)4(OH)6H2O8 (8)
dehydrate
-4H2O
Ag6Cl(atz)4(OH)2H2O8 (8)
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AgCl 3.053, 3.070 Å
4.3 ? 10.4 Å
Tetragonal P _at_ 293K (8)
6-fold interpenetration
Void 25.2
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Reversible structural changes
H2O
H2O
Dehydrated 4.3 ? 10.4 Å
Hydrated 7.8 ? 9.2 Å
Dynamic or Smart Porous Material
JACS, 2005, 14162
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One-pot synthesis of triazoles Cycloaddition of
Nitriles NH3 under hydro(solvo)thermal condition
Traditional synthetic methods multi-step,
hydrazine derivative based
Angew. Chem. Int. Ed. 2004, 43, 206
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4-connected nets based solely on square-planar
nodes
Cu(tz) Cu(mtz)
Cu(ptz)
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Cu6(etz)6guest (12) ????????
??????
????
??-????? ??? gt 300oC
JACS 2005, 127, 5495 JACS 2008, 130, 6010
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Cu(etz) (MAF-2) A porous material with
exceptional flexibilities and sorption properties
Flexible ethyl groups
d 1.5 Å
d lt 3.6 Å
gt 300oC
JACS 2005, 127, 5495
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Flexible Framework
21
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Traditional
Dynamic
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Multimode Guest-triggered Structural
Transformations
-
P1, V 1603 Å3
N2
-
R3, V 1580 Å3
-
-
R3, V 1561 Å3
-
R3, V 1591 Å3
R3, V 1606 Å3
-
D 0.1-1.3
Im3, V 1660 Å3
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Crystal Structures of MAF-2G
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A Dynamic Porous Magnet KCo7(OH)3(ip)6(H2O)4
(ip 1,3-phenyl-dicarboxylate)
Assembling magnetic anisotropic high-spin
clusters into 3D porous network
Multifunctional Material
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Co3 6-coordinate to 4-coordinate
N2 Sorption
Structural Change single-crystal to
single-crystal Transformation
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Guest-induced modulation effect of magnetic
properties
1
1
frequency dependence of the ac susceptibility
Hysteresis curves the temperature-dependent
susceptibility
Incorporating magnetic properties into porous
structure!
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??????(Secondary Building Units, SBUs)
???? ??? ??? ??? ???
4 6
6
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???????
MOF-500
MIL-100 MIL-101
MOF-236
MOF-235
G. Férey, et al. Acc. Chem. Res., 2005, 38, 217
O. M. Yaghi, Angew. Chem. Int. Ed. 2006, 45,
2528 Inorg. Chem. 2005, 44, 2998-3000.
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(No Transcript)
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???????(Supermolecular Triakis Tetrahedron)
void 21.2
d 9.3 Å 8.6 Å
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d 12.4 Å void 47.3 Total void 68.5
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Dynamic Porous Materials?
Smart Materials ?
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• ?????????,????????????????????
• ??0.3-2 nm,????????
• ????,???????(smart)
• ?????????????????(??),?????????
• ???
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