coordination polymers/ metal-organic frameworks...2001, 34, 319 oxtoby et al. pnas 2002, 99, 4905;...
TRANSCRIPT
![Page 1: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/1.jpg)
Coordination Polymers/
Metal-Organic Frameworks
Christoph Janiak
University of Düsseldorf, Germany
Email: [email protected]
![Page 2: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/2.jpg)
Periodic, extended architectures/framework structures
![Page 3: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/3.jpg)
Periodic, extended architectures/framework structures
collagen fiber from parallel
collagen fibrils:
function
![Page 4: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/4.jpg)
Periodic, extended architectures/framework structures,diatoms:
![Page 5: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/5.jpg)
Periodic, extended architectures/framework structures
Collembola
(springtails)
surface structure:
(tooth)
enamel prisms:
![Page 6: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/6.jpg)
Metal-organic networks / Coordination polymers
+
bridging organic ligand
M
M M M M1D chains
M M M
M M M
M M M
2D nets
M M M
M M M
M M MM
M M M
M M M
MM3Dframeworks
![Page 7: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/7.jpg)
From metal-organic networks
to hydrogen-bonded Networks
M
N
N D
A
MN
N
D
A
M
N
ND
A
M N
N
D
A
D = hydrogen donorA = hydrogen acceptor
Metal-organic networks H-bonded networks
M M M M1D chains
M M M
M M M
M M M
2D nets
M M M
M M M
M M MM
M M M
M M M
MM3Dframeworks
covalent
less flexible
more directional
network
electrostatic
more flexible
less directional
network
![Page 8: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/8.jpg)
Metal-organic networks:
Nodal properties of metal and ligands
M M
M M
Metal ions or metal-ligand fragments with free coordination sites
M M MM
bridging ligands
M M M
M M
M M
M
M
M
M
M
M
MM
M
M
M M
M
M
M
M M
M M
M
M
M
M
M
M
M
M
M
M
M
M
1D chain
2D net
3D framework
James,
Chem. Soc. Rev.
2003, 32, 276
Eddaoudi et al.,
Acc. Chem. Res.
2001, 34, 319
Oxtoby et al.
PNAS 2002,
99, 4905;
Eddaoudi et al.,
PNAS 2002,
99, 4901
![Page 9: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/9.jpg)
Coordination polymers:
Nodal properties of metal and ligands
M M
M M
Metal ions or metal-ligand fragments with free coordination sites
M M MM
bridging ligands
M M M
M M
M M
M
M
M
M
M
M
MM
M
M
M M
M
M
M
M M
M M
M
M
M
M
M
M
M
M
M
M
M
M
1D chain
2D net
3D framework
James,
Chem. Soc. Rev.
2003, 32, 276
Eddaoudi et al.,
Acc. Chem. Res.
2001, 34, 319
Oxtoby et al.
PNAS 2002,
99, 4905;
Eddaoudi et al.,
PNAS 2002,
99, 4901
![Page 10: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/10.jpg)
Coordination polymers:
Nodal properties of metal and ligands
M M
M M
Metal ions or metal-ligand fragments with free coordination sites
M M MM
bridging ligands
M M M
M M
M M
M
M
M
M
M
M
MM
M
M
M M
M
M
M
M M
M M
M
M
M
M
M
M
M
M
M
M
M
M
1D chain
2D net
3D framework
James,
Chem. Soc. Rev.
2003, 32, 276
Eddaoudi et al.,
Acc. Chem. Res.
2001, 34, 319
Oxtoby et al.
PNAS 2002,
99, 4905;
Eddaoudi et al.,
PNAS 2002,
99, 4901
![Page 11: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/11.jpg)
Metal-organic networks:
Nodal properties of metal and ligands
M M
M M
Metal ions or metal-ligand fragments with free coordination sites
M M MM
bridging ligands
M M M
M M
M M
M
M
M
M
M
M
MM
M
M
M M
M
M
M
M M
M M
M
M
M
M
M
M
M
M
M
M
M
M
1D chain
2D net
3D framework
James,
Chem. Soc. Rev.
2003, 32, 276
Eddaoudi et al.,
Acc. Chem. Res.
2001, 34, 319
Oxtoby et al.
PNAS 2002,
99, 4905;
Eddaoudi et al.,
PNAS 2002,
99, 4901
![Page 12: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/12.jpg)
N N
4,4'-bipyridine
N N
pyrazineO
OO
O
oxalate
O
OO
O
benzene-1,4-dicarboxylate,terephthalate
O O
O
O
O
O
benzene-1,3,5-tricarboxylate,trimesate
NN
N
N
hexamethylene-tetramine
N
O
O
isonicotinate
D
D
D
D
tetra(4-cyanophenyl)methanetetra(4-carboxyphenyl)methane
D = –CN
–CO2–
N
N
N
N
N
N2,4,6-tris(4-pyridyl)-1,3,5-triazine
Metal-organic networks:
Examples of linear, trigonal and tetrahedral ligands
linear rigid
trigonal
tetrahedral
(also
linear flexible
possible)
Oxtoby et al., PNAS 2002, 99, 4905; Kitagawa, Masaoka, Coord. Chem. Rev. 2003, 246, 73;
Barnett, Champness, Coord. Chem. Rev. 2003, 246, 145; Zheng et al., Coord. Chem. Rev. 2003, 246, 185;
Ye et al., Coord. Chem. Rev. 2005, 249, 545; Zhang, Chen, Chem. Commun. 2006, 1689
![Page 13: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/13.jpg)
Metal-organic networks / Metal-organic frameworks (MOFs):
Application-oriented properties
Dalton Trans.
(Review)
2003, 2781
Conductivity
Non-linear optics
M M... ...
M M... ...
M
...
...M... ...
...
...
M M... ...
M
...
M... ...
...
...
M
...
...
M... ...
M
...
M... ...
...
...
...
...
...
...
...
...
...
...
Catalysis
Chirality
Luminescence
Magnetism
Porosity
Zeolitic behavior
Spin-crossover
N N
O
O
O
O
O
OO
O
N N
O
O
O
O
OO
O
ON
N N
New J. Chem. 2010, 34, 2366
![Page 14: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/14.jpg)
Coordination polymers / Metal-organic frameworks (MOFs):
A dynamic field
New J. Chem. 2010, 34, 2366
![Page 15: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/15.jpg)
Interests in coordination polymers
crystal engineeringanion control
solvent control
ligands
architecture
helices
chirality
catalysis
hydrothermal synthesis
interpenetration
NLO-effects, -materials
polymorphism
(nano/micro-) porosity
zeolite analogs
molecular magnets
sensors
electrical conductivity
from structure to function
spin-crossover
noncovalent interactions
enantioselectivity
molecular sieves
![Page 16: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/16.jpg)
metal
ligandsupramolecular
interactions
solvent
anion
temperature
time stoichiometry
concentration
pH
periodicmolecular-based
architecture
reaction/crystallization conditions
Our approach:
From molecular building blocks to periodic, extended architectures
B
ABA
construction aspects:
![Page 17: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/17.jpg)
Crystallization from molecular building blocks in solution
B
A
solution
solvent
BA
solution
T
solvent/solution
reaction time, days
temperature
autoclave forhydrothermal synthesis
![Page 18: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/18.jpg)
Coordination polymers with
multidentate ligands
NN
NN
M M
N
N
N
N
N
N
N
N
NN
NN
M M
additional functionality,
framework structure with anchor groups
JCS Dalton Trans. 1999, 183; JCS Dalton Trans. 1999, 3121.
The concept:
N
N
N
N
NN
NN
N
NNC CN
BN
N
N
N
N
NNN
N
H
![Page 19: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/19.jpg)
Introduction
pyrazolylborate ligands
Trofimenko, Scorpionates, Imperial College Press, London 1999
N
B
N N
N
H
N
N
N
N
N
NB
HH
hydro-tris(pyrazolyl)borate dihydro-bis(pyrazolyl)borate
- molecular chelate complexes
KBH4 + n H-azolyl K[H4-nB(azolyl)n] + n H2
![Page 20: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/20.jpg)
Modified poly(pyrazolyl)borate ligands
N
B
N N
N
H
N
N
N
NN
N
NN
B
HH
tris(pyrazolyl)borate
bis(triazolyl)borate
N
N
B
N
N
H
N
N
tris(indazolyl)borate
N
B
N N
NNN
H
N
NN
N
NN
N
NN
NN
B
HH
tris(triazolyl)borate
bis(tetrazolyl)borate
Chem. Commun. 1994, 545; Chem. Eur. J. 1995, 1, 637; Z. Anorg. Allg. Chem. 2000, 626, 2053
![Page 21: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/21.jpg)
Modified poly(pyrazolyl)borate ligands
N
B
N N
N
H
N
N
N
NN
N
NN
B
HH
tris(pyrazolyl)borate
bis(triazolyl)borate
N
N
B
N
N
H
N
N
tris(indazolyl)borate
N
B
N N
NNN
H
N
NN
N
NN
N
NN
NN
B
HH
tris(triazolyl)borate
bis(tetrazolyl)borate
endodentate
chelating tometal atoms
molecularcomplexes
Chem. Commun. 1994, 545; Chem. Eur. J. 1995, 1, 637; Z. Anorg. Allg. Chem. 2000, 626, 2053
![Page 22: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/22.jpg)
Modified poly(pyrazolyl)borate ligands
N
B
N N
N
H
N
N
N
NN
N
NN
B
HH
tris(pyrazolyl)borate
bis(triazolyl)borate
N
N
B
N
N
H
N
N
tris(indazolyl)borate
N
B
N N
NNN
H
N
NN
N
NN
N
NN
NN
B
HH
tris(triazolyl)borate
bis(tetrazolyl)borate
exodentate
bridgingbetween
metal atoms
networks
Chem. Commun. 1994, 545; Chem. Eur. J. 1995, 1, 637; Z. Anorg. Allg. Chem. 2000, 626, 2053
![Page 23: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/23.jpg)
Coordination polymers from
modified poly(pyrazolyl)borato ligands
N
B
N N
NNN
H
N
NN
N
NN
N
NN
NN
B
HH
tris(triazolyl)borateN3
bis(tetrazolyl)borateN4
-0.19
-0.11 -0.09-0.13
-0.18
charge distribution(AM1-calculation)
![Page 24: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/24.jpg)
Coordination polymers with
modified poly(pyrazolyl)borate ligands
NN
NN
NN
B
N
MnMn
H2O
OH2
N
H2O
OH2
N
N
N
NN
N
NB
NH
N
N
HN
NN
N
NN
B
N
N N
N
N
NN
N
NB
NH
N
N
H
·4H2O
·4H2O
N
NN
N
NN
B
N
H
ZnZn
N
N
Zn
·1.5H2O
1D
Mn-N3
3D
Zn-N3
Chem. Eur. J. 1995, 1, 637.
JCS Dalton Trans. 1994, 2947.
![Page 25: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/25.jpg)
Mn-N3
water substructure
Chem. Eur. J. 1995, 1, 637.
![Page 26: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/26.jpg)
Mn-N3
C-H...O/N hydrogen bonding
Chem. Eur. J. 1995, 1, 637
Chem. Eur. J. 1996, 2, 991
Polyhedron 2002, 21, 553
![Page 27: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/27.jpg)
Zn-N3
linkage isomers
3-D coordination polymer
NN
NN
NN
B
NH
ZnZn
N
N
Zn
NB
N N
NNN
H
N
NN
B
N
NZn
N
NN
N
H
N
NN
Zn2+ + 2 N3-
days months
chelate complex
J. Chem. Soc. Dalton Trans. 1994, 2947
H2O H2O
6 H2O 1.5 H2O
kinetic product thermodynamic product
![Page 28: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/28.jpg)
Zn-N3
porous 3-D coordination polymer ?
![Page 29: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/29.jpg)
Zn-N3
porous 3-D coordination polymer ?
![Page 30: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/30.jpg)
Zn-N3
porous 3-D coordination polymer ?
![Page 31: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/31.jpg)
B
N
N N
H H
N
NN
Tl (Tl)
Tl Tl
Coordination polymers with
modified poly(pyrazolyl)borate ligands
N
NN
NN
N
N
NB
H
H
N
NN
NN
N
NNB
H
H
N
NN
NN
N
NN
NN
N
NN B
H
H
N
N
NB
H
H
M
OH2
H2O
M
M
M
OH2
H2O
OH2
H2O
OH2
H2O
OH H
OH H
M = Mn, Fe, Co (Ni, Cu), Zn, Cd
Polyhedron 2002, 21, 553.
Chem. Eur. J. 1995, 1, 637.
3D
2D
with bis(triazolyl)borate
continuing work by
Lobbia, Pettinari et al.
JCS Dalton Trans. 2002, 2333;
Inorg. Chim. Acta 2005, 358, 1162.
Youm et al., Bull. Kor. Chem. Soc.
2006, 27, 1521.
![Page 32: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/32.jpg)
Metal-N4
symmetric versus distorted grids
NN
N
NN
NN
N
BH
H
NN
N
N N
NN
N
BH
H
NN
N
NN
NN
N
NN
NN
N BH
H
NN
NB
H
H
M
M
M
M
NN
N
NN
NN
NB
H
H
NN
N
NN
NN
NBH
H
NN
N
NN
NN
N
NN
NN
N BH
H
NN
NB
H
H
M
M
M
M
M = Mn,Fe,Co,Zn,Cd M = Ni,Cu
NH3
H3N
NH3
H3N
NH3
H3N
NH3
H3N
OH2
H2O
OH2
H2O
OH2
H2
O
OH2
H2O
crystallization from H2O crystallization from NH3/H2O
aqua ligands ammine ligands
HO
H
HO
H
crystal water no crystal water
Chem. Eur. J. 1995, 1, 637
Chem. Ber. 1995, 128, 323
![Page 33: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/33.jpg)
Metal-N4
the water substructure as a reinforcing bar
Chem. Ber. 1995, 128, 323
![Page 34: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/34.jpg)
Ag-N3
from structure to function
space group: P 21cn (Pna 21)
N
NN
N
NN
B
N
H
Ag
Ag
Ag
N
Nfunction: 2nd order NLO effect (frequency doubling)
J. Am. Chem. Soc. 1996, 118, 6307
SHG signal intensity: 2 W/cm2
(1064 to 532 nm)
coefficient:
d33 = 1/2 ccc = (6±3)·10-15
m/V
indices of refraction:
(at 532 nm)
nc = 1.661
na = 1.584
structure: 2-D coordination polymer
![Page 35: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/35.jpg)
Metal-organic networks:2[Ag(µ-HB(C2H2N3)3]
Non-linear optics b
a
c
1064 nm
532 nm non-centrosymmetric
space group: Pna 21
N
NN
N
NN
B
NH
Ag
Ag
Ag
N
N
JACS 1996, 118, 6307
SHG: 2 W/cm2
d33 = 1/2 ccc = (6±3)·10–15 m/V
![Page 36: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/36.jpg)
Metal-organic networks:
Non-linear optics
Non-linear optics
NCO2
–
N
CO2–
NCO2
–
N
CO2–
N CO2– N
CO2–
+ Zn2+
, Cd2+
Evan, Lin,
Acc. Chem. Res. 2002, 35, 211
Dalton Trans. 2003, 2781
![Page 37: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/37.jpg)
Coordination polymers with multidentate ligands
NN
NN
M M
N
N
N
N
N
N
N
N
NN
NN
M M
additional functionality
framework structure with anchor groups
N
N
N
N
N N
N
N
N
N
N
N
NC CN
N N
J. Chem. Soc., Dalton Trans. 1999, 183
Synthesis 1999, 959
Synth. Commun. 1999, 29, 3341
![Page 38: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/38.jpg)
N
NNC CN
5,5'-dicyano-2,2'-bipyridine
N NNC CN
+ Ag-saltsvariation of anionvariation of solvents
?
Coordination polymers
with modified 4,4'-bipyridine ligands
J. Chem. Soc., Dalton Trans. 1999, 183
![Page 39: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/39.jpg)
Coordination polymers with multidentate ligands:
Control elements for metal-ligand coordination
chelating
bidentate tetradentatetridentate
N N
AgN N
Ag
N N
Ag
NC CN
N NNC CN
NC CN
NCanion
Ag
1D-chain
NC CN AgAg
CN NC
2D-netanion
anion
J. Chem. Soc., Dalton Trans. 1999, 183
"non"-coordinating
BF4–, PF6
–coordinating
NO3–, CF3SO3
–"non"-coordinating
PF6–
solvent
EtOH/THF
or
MeCN/EtOH/CH2Cl2
solvent
MeCN/EtOH/
toluene
![Page 40: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/40.jpg)
Coordination polymers:
Effect of solvent changes
molecular chelatecomplex
2D coordination polymer
N N
AgN N
Ag
NC CN
N NNC CN
NC CN AgAg
CN NC
2D-netanion
anion
J. Chem. Soc., Dalton Trans. 1999, 183
"non"-coordinating
BF4–, PF6
–"non"-coordinating
PF6–
Understanding?
Design at will?
solvent
EtOH/THF
or
MeCN/EtOH/CH2Cl2
solvent
MeCN/EtOH/
toluene
![Page 41: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/41.jpg)
32.62 Kagomé net
2D Coordination polymer:2[Ag(µ3-L)]PF6·1/2C6H5CH3
J. Chem. Soc., Dalton Trans. 1999, 183
![Page 42: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/42.jpg)
32.62 Kagomé net
2D Coordination polymer:2[Ag(µ3-L)]PF6·1/2C6H5CH3
J. Chem. Soc., Dalton Trans. 1999, 183
![Page 43: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/43.jpg)
Coordination polymers
with modified 4,4'-bipyridine ligands
N
N
N
N
N N
NN
NN
4,4'-bipyridine
2,2'-dimethyl-4,4'-bipyrimidine
2,2'-bi-1,6-naphthyridine
Synthesis, 1999, 959
charge distribution(AM1 calculation)
-0.16
-0.18
-0.14-0.13
![Page 44: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/44.jpg)
+ M-saltsvariation of Mvariation of anionvariation of conditions
?
NN
NN
2,2'-dimethyl-4,4'-bipyrimidine
NN
NN
Coordination polymers
with modified 4,4'-bipyridine ligands
J. Chem. Soc., Dalton Trans. 1999, 3121
![Page 45: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/45.jpg)
CuII
CuI
AgI
Coordination polymers with multidentate ligands:
Control elements for metal-ligand coordination
chelatingbidentate tetradentate
bridgingtridentate
NN N
N
M
NN N
N
M
MMNN N
N
M
MNN
NN
MM
J. Chem. Soc. Dalton Trans. 1999, 3121
M = NiII
CuI
CuI
metal
AgI
+ Cl–/OH2
+ I–
+ NO3–
+ I–
+ PF6–
+ PF6–
+ NO3–
(1:1)
coordinating anion "non"-coordinating anion
+ heat + RT
different thermal treatment
Bodar-Houillon et al.,
Inorg. Chem.
1995, 34, 5205
![Page 46: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/46.jpg)
2[Cu2(µ3-I)2(µ-L)]
![Page 47: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/47.jpg)
2[Cu2(µ3-I)2(µ-L)]
![Page 48: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/48.jpg)
2[Ag3(NCCH3)3(µ3-L)](PF6)3
63 net
![Page 49: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/49.jpg)
2[Ag3(NCCH3)3(µ3-L)](PF6)3
63 net
![Page 50: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/50.jpg)
Coordination polymers with multidentate ligands
NN
NN
M M
N
N
N
N
N
N
N
N
NN
NN
M M
additional functionality
framework structure with anchor groups
N
N
N
N
N N
N
N
N
N
N
N
NC CN
N N
![Page 51: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/51.jpg)
N
N
N
N
M
M
M = CoII, ZnII, CdII
N NN N M
M
"non"-coordinating anion
CuI+ PF6–+ NCS–
coordinating anion
Coordination polymers with multidentate ligands:
Control elements for metal-ligand coordination
Chem. Commun. 1998, 2637
2,2'-bi-1,6-naphthyridine
bidentate bridging tridentate
![Page 52: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/52.jpg)
2-D Coordination polymers with binaphthyridine:
Interpenetration
N
N
N
N
M
M
M = CoII, ZnII, CdII
N
N
N
N
N
N
N
N
N
N
N
N
M
M
NCS
NCS
NCS
SCN
SCN
SCN
SCN
NCS
15.8 - 16 Å
M
M
M
M
=
M
M
N
N
N
N
Chem. Commun. 1998, 2637
![Page 53: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/53.jpg)
2-D coordination polymers with binaphthyridine
interpenetration
3.25 Å
N
N
N
N M
M
NCS
SCN
Chem. Commun. 1998, 2637
![Page 54: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/54.jpg)
2-D coordination polymers with binaphthyridine
interpenetration
3.25 Å
N
N
N
N M
M
NCS
SCN
Chem. Commun. 1998, 2637
![Page 55: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/55.jpg)
Interpenetration
1D 1D 3D 3D
3D 3D 3D 3D
Batten, Robson,
Angew. Chem. Int. Ed. 1998, 37, 1460
Carlucci, Ciani, Proserpio
2D 2D 2D 2D
![Page 56: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/56.jpg)
Coordination polymers:
Spin-crossover
Spin-crossover
N N
N
R
N NNR
N N
N
R
Fe Fe
N N
N
R
N NNR
N N
N
R
Fe
N N
N
R
N NNR
N N
N
R
Fe
N N
N
R
N NNR
N N
N
R
FeFe Fe
d6
1A1g,
low-spin
5T2g,
high-spin
NFe
N N
N
N
N
FeII
(eg)
(t2g)
Temp. increase,green light,
pressure decrease
Temp. decrease,red light,
pressure increase
van Koningsbruggen,
Top. Curr. Chem.
2004, 233, 123.
Dalton Trans.
(Review)
2003, 2781.
Haasnoot,
Coord. Chem. Rev.
2000, 200–202, 131.
![Page 57: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/57.jpg)
N
N
N
N
+ Fe2+
+ NCS–
+ EtOH
Coordination polymers:
Spincrossover
Spin-crossover
Kepert et al.,
Science 2002, 298, 1762
Porosity
![Page 58: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/58.jpg)
Coordination polymers:
Spin-crossover – cooperative behavior
N N
N
R
N NNR
N N
N
R
Fe Fe
N N
N
R
N NNR
N N
N
R
Fe
N N
N
R
N NNR
N N
N
R
Fe
N N
N
R
N NNR
N N
N
R
FeFe Fe
Gütlich et al.,
Eur. J. Inorg. Chem. 2007, 4481.
Example of recent work:
N N
N
HN O
tba
[{Fe(tba)3}X2]·nH2O
![Page 59: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/59.jpg)
N
NN
NN
N
btre1,2-bis(1,2,4-triazol-4-yl)ethane
N
NN
NN
NM
M
M
M
possiblebridging mode:
Metal-organic networks
with bridging bis(1,2,4-triazolyl)-ligands
Our choice:
spin-crossover,
magnetic interactions
with appropriate
metal atoms
rarely used so far: 2{M(NCS)2(µ2-btre-kN1,N1')2(NCS)2} (M = Fe, Co)
3{[Cu3(µ4-btre-kN1,N2,N1',N2')2(µ3-btre-kN1,N2,N1')4(H2O)2]2(ClO4)12·2H2O}
Garcia, Gütlich et al., Inorg. Chem. 2005, 44, 9723.
Garcia, Haasnoot, Kahn et al. Eur. J. Inorg. Chem. 2000, 307.
![Page 60: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/60.jpg)
N
N
N
NN
N
1,2-bis(1,2,4-triazol-1-yl)ethane
1,4-bis(1,2,4-triazol-1-yl)butane
M
M
N
NNN N
NM
M
N
N
NN
NN
MM
1,4-bis(1,2,4-triazol-1-ylmethyl)benzene
1,3-bis(1,2,4-triazol-1-yl)propane
N NN
N NNM M
etc.
Metal-organic networks
with bridging bis(1,2,4-triazol-1-yl)-ligands
Examples of recent work:
Zhu et al., J. Coord. Chem. 2006, 59, 513.
Wang et al., Chem. Eur. J. 2006, 12, 2680.
Frequently used bis-triazolyl ligands:
Wang et al., Acta Cryst. 2007, E63, m2416.
Peng et al., Cryst. Growth&Des. 2006, 6, 994.
Tian et al., Inorg. Chem. 2008, 47, 3274.
![Page 61: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/61.jpg)
fluconazole
N NN
N NN M
OH
M
F
F
M M
Metal-organic networks
with bridging bis(1,2,4-triazolyl)-ligands
Frequently used bis-triazolyl ligands:
Li, Ma, Su et al., Dalton Trans. 2008, 3824.
Dalton Trans. 2008, 2015.
Inorg. Chem. 2007, 46, 8283.
Han et al., Eur. J. Inorg. Chem. 2006, 1594.
N
NN
NN
N
btre1,2-bis(1,2,4-triazol-4-yl)ethane
![Page 62: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/62.jpg)
Metal-organic networks
with 1,2-bis(1,2,4-triazol-4-yl)ethane
N
NN
NN
N H2O, 180 °C, 3d ZnX2
CuX2
CdX2
X = Cl, Br, ClO4, (SO4)1/2
Cu(II) Cu(I)
0D, 1D, 2D, 3D networks
![Page 63: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/63.jpg)
Metal-organic networks
with 1,2-bis(1,2,4-triazol-4-yl)ethane
N
NN
NN
N H2O, 180 °C, 3d X = Cl, Br, ClO4, (SO4)1/2
Cu(II) Cu(I)
0D, 1D, 2D, 3D networks
Example for 1D:
ZnX2
CuX2
CdX2
![Page 64: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/64.jpg)
Metal-organic networks
with 1,2-bis(1,2,4-triazol-4-yl)ethane
N
NN
NN
N H2O, 180 °C, 3d X = Cl, Br, ClO4, (SO4)1/2
Cu(II) Cu(I)
0D, 1D, 2D, 3D networks
Example for 1D:
ZnX2
CuX2
CdX2
- - - interstrand C-H···N
Inorg. Chem. 2009, 48, 2166.
![Page 65: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/65.jpg)
Metal-organic networks
with 1,2-bis(1,2,4-triazol-4-yl)ethane
N
NN
NN
N H2O, 180 °C, 3d X = Cl, Br, ClO4, (SO4)1/2
0D, 1D, 2D, 3D networks
Example for 2D:
Cu(II) Cu(I)
2D 2[Cu2(µ2-Cl)2(µ4-btre)]
ZnX2
CuX2
CdX2
![Page 66: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/66.jpg)
Metal-organic networks
with 1,2-bis(1,2,4-triazol-4-yl)ethane
N
NN
NN
N H2O, 180 °C, 3d X = Cl, Br, ClO4, (SO4)1/2
0D, 1D, 2D, 3D networks
Example for 2D:
Cu(II) Cu(I)
2D 2[Cu2(µ2-Cl)2(µ4-btre)]- - - interlayer C-H···Cl
-stacking
ZnX2
CuX2
CdX2
Inorg. Chem. 2009, 48, 2166.
![Page 67: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/67.jpg)
Metal-organic networks
with 1,2-bis(1,2,4-triazol-4-yl)ethane
N
NN
NN
N H2O, 180 °C, 3d X = Cl, Br, ClO4, (SO4)1/2
0D, 1D, 2D, 3D networks
Examples for 3D:
Cu(II) Cu(I)
3D 3{[Cu(µ4-btre)]ClO4 · ~0.25H2O}
ClO4–, H2O
ZnX2
CuX2
CdX2
Inorg. Chem. 2009, 48, 2166.
![Page 68: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/68.jpg)
Metal-organic networks
with 1,2-bis(1,2,4-triazol-4-yl)ethane
N
NN
NN
N H2O, 180 °C, 3d X = Cl, Br, ClO4, (SO4)1/2
Cu(II) Cu(I)
0D, 1D, 2D, 3D networks oxidative ligand decomposition
formation of cyanide
3D interpenetrated nets
3D 3[Cu2(µ2-CN)2(µ4-btre)]
ZnX2
CuX2
CdX2
Inorg. Chem. 2009, 48, 2166.
![Page 69: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/69.jpg)
Metal-organic networks
with 1,2-bis(1,2,4-triazol-4-yl)ethane
N
NN
NN
N H2O, 180 °C, 3dZnX2
CuX2
X = Cl, Br, ClO4, (SO4)1/2
Cu(II) Cu(I)
0D, 1D, 2D, 3D networks oxidative ligand decomposition
formation of cyanide
3D interpenetrated nets
interpenetration control through stacking
Inorg. Chem. 2009, 48, 2166.
![Page 70: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/70.jpg)
1,2-bis(1,2,4-triazol-4-yl)ethane networks:
Structure – solid-state CPMAS 13C NMR correlation
N
NCH
N
HC
CH2
NN
NM
M
M
M
![Page 71: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/71.jpg)
1,2-bis(1,2,4-triazol-4-yl)ethane networks:
Structure – solid-state CPMAS 13C NMR correlation
(bold = occ. fact. 1)
N
NCH
N
HC
CH2
NN
NM
M
M
M
N
NCH
N
HC
CH2
H2C N
CH
N
N
HC
M
M
M
M
+
Inorg. Chem. 2009, 48, 2166.
![Page 72: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/72.jpg)
1,2-bis(1,2,4-triazol-4-yl)ethane networks:
Structure – solid-state CPMAS 13C NMR correlation
(bold = occ. fact. 1)
(normal = occ. fact. 0.5)
N
NCH
N
HC
CH2
NN
NM
M
M
M
N
NCH
N
HC
CH2
H2C N
CH
N
N
HC
M
M
M
M
+
N
NCH
N
HC
CH2
H2C N
N
N
HC
M
M
+
![Page 73: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/73.jpg)
Metal-organic networks / Metal-organic frameworks (MOFs):
Porosity and zeolitic behavior
M M M
M M M
M M MM
M M M
M M M
MM
M M M
M M M
M M MM
M M M
M M M
MM
Zeolitic behaviorPorosity
– ab/desorption, gas storage
– ion exchange
– enantiomer separation
– selective catalysis
Eddaoudi et al., Acc. Chem. Res. 2001, 34, 319;
Kesanli, Lin, Coord. Chem. Rev. 2003, 246, 305;
Rao et al., Angew. Chem. Int. Ed. 2004, 43, 1466;
Kitagawa et al., Angew. Chem. Int. Ed. 2004, 43, 2334;
Kitagawa, Uemura, Chem. Soc. Rev. 2005, 34, 109;
Rowsell, Yaghi, Angew. Chem. Int. Ed. 2005, 44, 4670;
Mueller et al., J. Mater. Chem. 2006, 16, 626;
Kepert, Chem. Commun. 2006, 695;
Kitagawa et al. Chem. Commun. 2006, 701;
![Page 74: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/74.jpg)
O O
OO
Metal-organic networks / Metal-organic frameworks (MOFs):
Porosity and zeolitic behavior
Zeolitic behaviorPorosity
+ {Zn4(µ4-O)(MeOH)4}
O. M. Yaghi et al., Science 2002, 2003
Rowsell, Yaghi, Angew. Chem. Int. Ed., 2005, 117, 4670
Schröder, Champness et al., CrystEngComm, 2007, 9, 438
CH4, H2 storage
![Page 75: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/75.jpg)
Mixed-ligand metal-organic networks:3{[Ni3(µ3-L1)2(µ4-L2)2(µ-H2O)2]·~22H2O}
N
NN
NN
NL2 =
O
–O
O–
O
O–OL1 =
potential solvent volume
1621 Å3/unit cell
= 52%
(H2O ~40 Å3)
Porosity ?
Dalton Trans. 2008, 1734
![Page 76: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/76.jpg)
Mixed-ligand metal-organic networks:3{[Ni3(µ3-L1)2(µ4-L2)2(µ-H2O)2]·~22H2O}
N
NN
NN
NL2 =
O
–O
O–
O
O–OL1 =Porosity ?
Dalton Trans. 2008, 1734
P21/c
R1/wR2 [>2(I)] 0.0398 / 0.1076
R1/wR2 (all) 0.0473 / 0.1125
Some of the disordered O positions refined isotropically
with "anti-bumping" restraints (BUMP).
Occupancies refined to about 0.15, 0.30, 0.60, 0.90 and 1.000,
summed up to 22 O atoms per Ni3
![Page 77: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/77.jpg)
3{[Ni3(µ3-L1)2(µ4-L2)2(µ-H2O)2]·~22H2O} – careful drying
3{[Ni3(µ2-L1)2(µ4-L2)2(µ-H2O)2(H2O)2]·4H2O}
Porosity ?
solid state crystal to-
crystal transformation
under vacuum
Porosity
N
NN
NN
NL2 =
O
–O
O–
O
O–OL1 =
but ...
Dalton Trans. 2008, 1734.
P21/c
b = 13.5328(2) Å
b = 8.2320(5) Å
![Page 78: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/78.jpg)
Mixed-ligand coordination polymers:3{[Zn3(µ4-L1)2(µ4-L2)2(H2O)2]·2H2O}
potential solvent volume
94 Å3/unit cell
= 7%
(H2O ~40 Å3)
N
NN
NN
NL2 =
O
–O
O–
O
O–OL1 =
Porosity ?
Dalton Trans. 2008, 1734.
![Page 79: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/79.jpg)
3{[Zn3(µ4-L1)2(µ4-L2)2(H2O)2]·2H2O} – careful drying
3{[Zn3(µ5-L1)2(µ4-L2)2]·~0.67H2O}
Porosity ?
solid state
single-crystal
to-single-crystal
transformation
between 100-280 °C
Porosity
N
NN
NN
NL2 =
O
–O
O–
O
O–OL1 =
Dalton Trans. 2008, 1734.
![Page 80: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/80.jpg)
Mixed-ligand metal-organic networks:3{[Ni3(µ3-L1)2(µ4-L2)2(µ-H2O)2]·~22H2O}
N
NN
NN
NL2 =
O
–O
O–
O
O–OL1 =but ...
flexible framework,
dynamic porous properties
150 °C/12 hPa
40 °C/56 hPa
–H2O
+H2O
for dynamic porous properties, see Kitagawa, Uemura, Chem. Soc. Rev. 2005, 34, 109.
Stefan Henninger
J. Am. Chem. Soc. 2009, 131, 2776.
![Page 81: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/81.jpg)
Principle process in an adsorption chiller
Stefan Henninger
J. Am. Chem. Soc. 2009, 131, 2776.
![Page 82: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/82.jpg)
Adsorption chillers: Water loading lifts
Stefan Henningerzeolites
J. Am. Chem. Soc. 2009, 131, 2776.
![Page 83: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/83.jpg)
Metal-organic networks:
Magnetism
Magnetism
organic ligands for stronger magnetic coupling:
nitronyl nitroxide
radical
N NO O
R
N
M M
N
pyrazolate
O
M M
O
R
carboxylate
N N
N N
M M
2,2'-bipyrimidine
O O
O O
M M
oxalate
M M
Batten, Murray,
Coord. Chem. Rev.
2003, 246, 103.
Maspoch et al.,
J. Mater. Chem.
2004, 14, 2713.
Maspoch, et al,
Chem. Soc. Rev.,
2007, 36, 770.
![Page 84: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/84.jpg)
Metal-organic networks:
Magnetism
Magnetism
organic ligands for stronger magnetic coupling:
nitronyl nitroxideradical
N NO O
R
N
M M
N
pyrazolate
O
M M
O
R
carboxylate
N N
N N
M M
2,2'-bipyrimidine
O O
O O
M M
oxalate
M M
N N
N
M M
triazolate
N N
N
M M
triazole
RM
Batten, Murray,
Coord. Chem. Rev.
2003, 246, 103
Maspoch et al.,
J. Mater. Chem.
2004, 14, 2713
Maspoch, et al,
Chem. Soc. Rev.,
2007, 36, 770
![Page 85: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/85.jpg)
Metal-organic networks:
Magnetism
Magnetism
= Mn(II) = Cr(III)
anionic net: [MIIMIII(ox)3]–C
CO
OO
O
Example:
Dalton Trans.
2003, 2781
Batten, Murray,
Coord. Chem. Rev.
2003, 246, 103
Maspoch et al.,
J. Mater. Chem.
2004, 14, 2713
Maspoch, et al,
Chem. Soc. Rev.,
2007, 36, 770
![Page 86: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/86.jpg)
Metal-organic networks:
Magnetic interactions based on triazole ligands
NN
N
CuCu
N
Cl(Br)
Example of recent work:
Drabent et al., Inorg. Chem. 2008, 47, 3358.
{[Cu(μ-OH)(μ-ClPhtrz)][(H2O)(BF4)]}n
ClPhtrz
![Page 87: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/87.jpg)
Metal-organic networks
constructed from triazolate ligands
N N
N
M M
triazolate
M
RR
Zhang, X.M. Chen, Chem. Commun.
(Review) 2006, 1689.
also
Barea, Sironi et al., Dalton Trans. 2008, 1825,
R = H
R = Et
Recent examples
R2tz –
{Cu(H2tz)}n
{Cu(Et2tz)}n
![Page 88: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/88.jpg)
Magnetism
Mixed-ligand metal-organic networks:3{[Ni3(µ3-L1)2(µ4-L2)2(µ-H2O)2]·~22H2O}
intra-Ni3 trimer antiferromagnetic coupling with J = –13.88(8) cm–1
O
–O
O–
O
O–OL1 =
N
NN
NN
NL2 =
Dalton Trans. 2008, 1734.
![Page 89: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/89.jpg)
Mixed-ligand metal-organic networks:3{[Cu4(µ5-L1)2(µ3-OH)2(µ4-L2)]·2H2O}
Cu1Cu2'
Cu2Cu1'
2J32J1
2J2
2J2
2J3
chair-shaped or
stepped-cubane Cu4O4
2J1 = 258 cm–1,
2J2 = –416 cm–1,
2J3 = 484 cm–1
antiferromagnetic coupling, three pathways
with Joaquin Sanchiz
Magnetism
![Page 90: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/90.jpg)
2∞[Cu2(µ5-btb)(µ-OH)(µ-H2O)]
with ferromagnetically coupled Cu2 units
J
J
j3
j2
J
j3
j2
J
j3
j2
Cu1
Cu1
Cu1
Cu1
Cu2
Cu2
Cu2
Cu2
Magnetism
J = 83(1) cm–1
j2 = 0.161(1) cm–1
O–
O
O–Obtb =
O
O–
with J. Sanchiz, Dalton Trans. 2008, 4877.
![Page 91: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/91.jpg)
Metal-organic networks:
Luminescence
Zn
Ag Cd
Au
Coordination polymers with
Eu Gd Tb
Dalton Trans. 2003, 2781
Zheng, Chen, Aust. J. Chem. 2004, 57, 703
LMCT
LLCT
ff
Luminescence
![Page 92: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/92.jpg)
Mixed-ligand metal-organic networks :3{[Zn3(µ4-L1)2(µ4-L2)2(H2O)2]·2H2O}
Luminescence
N
NN
NN
NL2 =
O
–O
O–
O
O–OL1 =
Dalton Trans. 2008, 1734
![Page 93: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/93.jpg)
Mixed-ligand coordination polymers:2∞{[Cu2(µ-L-tryptophanato)2(µ-4,4'-bipyridine)(H2O)2](NO3)2}
L2 =
NH2
O
–O
L1 =
N N
N
* S
Chirality
![Page 94: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/94.jpg)
Mixed-ligand coordination polymers:2∞{[Cu2(µ-L-tryptophanato)2(µ-4,4'-bipyridine)(H2O)2](NO3)2}
Chirality
L2 =
NH2
O
–O
L1 =
N N
N
* S
![Page 95: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/95.jpg)
Coordination polymers as catalysts
Lit.: [RuCl2(PPh3)3]
[RuCl2(L)3/2]
L = P P
OOH
+
OHO
+
NaOH
HH
Catalysis
[RuCl2(PPh3)3]: R. L. Chowdhury, J.-E. Bäckvall, Chem. Commun. 1991, 1063.
![Page 96: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/96.jpg)
3 .5 0 4 .0 0 4 .5 0 5 .0 0 5 .5 0 6 .0 0 6 .5 00
5 0 0 0 0
1 0 0 0 0 0
1 5 0 0 0 0
2 0 0 0 0 0
2 5 0 0 0 0
3 0 0 0 0 0
3 5 0 0 0 0
4 0 0 0 0 0
4 5 0 0 0 0
T im e -->
A b u n d a n c eT IC : T H O M A S 1 5 .D
OHH
t = 1.5 h
O
O+Toluol
(int. stand.)
3 .5 0 4 .0 0 4 .5 0 5 .0 0 5 .5 0 6 .0 0 6 .5 00
5 0 0 0 0
1 0 0 0 0 0
1 5 0 0 0 0
2 0 0 0 0 0
2 5 0 0 0 0
3 0 0 0 0 0
3 5 0 0 0 0
4 0 0 0 0 0
T im e -->
A b u n d a n c eT IC : T H O M A S 1 9 .D
t = 7.5 h
[RuCl2(L)3/2]
L =
P P
/NaOH
– GC-MSOHH
0
10
20
30
40
50
60
70
80
90
100
0 5 10Time [h]
Co
nv
ers
ion
[%
]
Coordination polymers as catalysts
Catalysis
![Page 97: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/97.jpg)
catalyst recycling after t = 6 h
[RuCl2(L)3/2]OOH
+
OHO
+
NaOH
HH
[RuCl2(L)3/2]
L =
P P
/NaOH
0
10
20
30
40
50
60
70
80
90
100
0 1 2 3 4 5 6 7 8 9 10 11
Recycling [no.]
Co
nv
ers
ion
[%
]Recycling Exp A
Recycling Exp B
Coordination polymers as catalysts
Catalysis
![Page 98: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/98.jpg)
O
OO
O
HNO
N
Zn2+
- homochiral- chiral 1D channels- 47% free volume
+ ROH CH3C(O)OR +
2{[2H3O][Zn3(µ3-O)L6]·12H2O}
O2N
NO2CH3C(O)O
O2N
NO2HOA
A= L
**
Coordination polymers:
Catalysis and chirality
Porosity
Catalysis Chirality
Zeolitic behavior
Kim et al., Nature 2000, 404, 982
Kesanli, Lin,
Coord. Chem. Rev.
2003, 246, 305
Dalton Trans. 2003, 2781
![Page 99: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/99.jpg)
Summary:
Metal-organic networks
N
NN
NN
N
N
NN
NN
NL2 =
O
–O
O–
O
O–OL1 =
mixed-ligand
1,2-bis(1,2,4-triazol-1-yl)ethane
O–
O
O–O
O
O–
benzene-1,2,3-carboxylate
Magnetism
structure – CPMAS 13C NMR correlation
Luminescence
crystal-to-
crystal
transition
![Page 100: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/100.jpg)
Summary:
Metal-organic networks
N
NN
NN
N
N
NN
NN
NL2 =
O
–O
O–
O
O–OL1 =
mixed-ligand
1,2-bis(1,2,4-triazol-1-yl)ethane
crystal-to-
crystal
transition
![Page 101: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/101.jpg)
Summary:
Metal-organic networks: Application-oriented properties
Conductivity
Non-linear optics
M M... ...
M M... ...
M
...
...M... ...
...
...
M M... ...
M
...
M... ...
...
...
M
...
...
M... ...
M
...
M... ...
...
...
...
...
...
...
...
...
...
...
Catalysis
Chirality
Luminescence
Magnetism
Porosity
Zeolitic behavior
Spin-crossover
N N
O
O
O
O
O
OO
O
N N
O
O
O
O
OO
O
ON
N N
![Page 102: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/102.jpg)
Summary:
Metal-organic networks: Application-oriented properties
Conductivity
Non-linear optics
M M... ...
M M... ...
M
...
...M... ...
...
...
M M... ...
M
...
M... ...
...
...
M
...
...
M... ...
M
...
M... ...
...
...
...
...
...
...
...
...
...
...
Catalysis
Chirality
Luminescence
Magnetism
Porosity
Zeolitic behavior
Spin-crossover
O
O
O
O
OO
N
B
N N
NNN
H
N
NN
N N
N
N
NN
NN
N
N N
N
R
![Page 103: Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905; Eddaoudi et al., PNAS 2002, 99, 4901. N N 4,4'-bipyridine N N pyrazine O O O O oxalate](https://reader030.vdocuments.us/reader030/viewer/2022040810/5e51887348e567725f77ba37/html5/thumbnails/103.jpg)
Acknowledgements
CPMAS NMR Dr. Anke Hoffmann, Univ. Freiburg
Magnetism Prof. J. Sanchiz, Univ. La Laguna
Mössbauer Dr. H. Winkler, Univ. Lübeck
TG/MS PD Dr. C. Näther, Univ. Kiel
Neutron diffraction Dr. S. Mason, ILL Grenoble
Heat transformation S. Henninger, ISE Freiburg
Luminescence Dr. H. Höppe, Univ. Freiburg
special X-ray Prof. C. Röhr, Univ. Freiburg
NP-TEM Dr. R. Thomann, Univ. Freiburg
Au-NP Dr. M. Krüger, Dr. M. Walter, Univ. Freiburg
Finances: DFG, FCI, AvH
Dr. Khalid Abu-Shandi
Frederik Blank
Anne-Christine Chamayou
Stefan Deblon
Dr. Thomas Dorn
Prof. Dr. M. Enamullah (AvH)
Marie Genitrini
Jerôme Krämer
Dr. Paul G. Lassahn
Hesham Mena
Dr. Barbara Wisser (née Paul)
Engelbert Redel
Dr. Tobias Scharmann
Dr. Savas Temizdemir
Lars Uehlin
Jana Vieth
Christian Vollmer
Dr. Biao Wu
Dr. He-Ping Wu (AvH)
Dr. Xiao-Juan Yang
Dr. Cungen Zhang (AvH)