第五届全国物理无机化学会议——鲁统部.

Zhou et al, J. Am. Chem. Soc. 2008, 130, 1012.
Method 2.The use of rigid planar ligands containing multiple coordination sites.
Chen et al, J. Am. Chem. Soc. 2008, 130, 6010.
100
b
80
60
40
10 20
0 0
0.0 0.2 0.4 0.6 0.8 1.0 P/Po
0.0
0.2
Adsorption Desorption
0.4
0.6
0.8
1.0
P/Po
H NN
M(II) +
NN
COOC2H5 (ETZc)
in situ metal/ligand reactions
Zn(Ac)2·2H2O
Pore sizes = 4.9 × 4.9 Å
acs topological net
Larger pore size: 30~34 Å; Langmuir surface area for N2: ~5900 m2/g Ferey et al, Acc. Chem. Res. 2005, 38, 217; Science, 2005, 309, 2040
Langmuir surface area: 2178 m2/g High methane uptake
Catalysis the reaction of CO to CO2
Xu et al, Angew. Chem. Int. Ed. 2006, 45, 2542.
{([In48(HIDC)96]48-)}n
Eddaoudi et al, Chem. Commun. 2006, 1488.
HN O
M21L12 cage
J. Am. Chem. Soc. 2006, 128, 34.
2 of 3
Hexagonal closest packing as A3-type metal
HN N H
O
O + Zn2+
OO H
bpy py
[Zn3(IDC)2(bpy)3](bpy)8H2O
Cryst. Growth Des., 2006, 6, 564.
CuCl2·2H2O
Cd(NO3)2·4H2O
Cu(NO3)2·4H2O
[Zn3(Tz)6(H2O)2] n [Cu2(Tz)3(OH)] n {[Cd5(Tz)9](NO3)·8H2O} n {[Cu5(Tz)9](NO3)·8H2O} n
The kagomédual topology net
fsc topological net
1000
500
-OHH2O [Hprz]+
Inorg Chem., 2007, 46, 5835.
HN N H
Cd(NO3)2 + O
O +N
OO H
pyridine
pyridine
N
KOH
KOH
2:1:2 1:1:1 2:1:1 4:1:2
1
2
3
4
Cryst. Growth Des., 2008, 8, 986.
Eddaoudi et al,, J. Am. Chem. Soc. 2009, 131, 10394.
Kitagawa et al, Chem. Commun. 2005, 2436 Yang et al, Angew. Chem. Ent. Ed. 2005, 44, 2553.
Na20Ni8L12
Relatived Intensity (a. u.)
2,3-吡嗪二羧酸 + Cd2+
Bpy py
[Cd2(PZDC)2(bpy)2]
窗口大小2.2 × 4.6 Å
A/cm3(STP)g-1 A / mg g-1
50 a
40 30 20
77K, N2, Adsorption 77K, N2, Desorption 195 K, CO2, Adsorption 195 K, CO2, Desorption
as-synthesized 500C 1000C 2000C
3000C 3400C 3600C 3800C
10
20
30
40
50
2Theta (deg)
xylene toluene benzene acetone methanol as-synthesized
3500
3000
2500
2000
1பைடு நூலகம்00
利用多配位点平面配体构筑孔状 配位聚合物
鲁统部
中山大学化工学院 2009年9月 汕头
The construction of porous MOFs
Method 1.The use of large secondary building units as vertices
Yaghi et al, Science 2002, 295, 469.
N
H O
+
Cd2+
OO H
pH = 8
Bpy py
(H2bpy)[Cd9(HIDC)4(IDC)4(bpy)4]
Cryst. Growth Des., 2006, 6, 564.
HN O
N
H O
+
Cd2+
pH = 10
bpy or
OO H
Bu4N+
Na4Cd7(IDC)63bpy7H2O (Bu4N)K3Cd7(IDC)66H2O
8000 7000 6000 5000 4000 3000 2000 1000
0
Inorg Chem., 2009, 48, 6997.
No addition
3 Equiv Na+ 3 Equiv NH +
4
3 Equiv Mg2+ 3 Equiv Ca2+ 3 Equiv Sr2+ 3 Equiv Ba2+ 3 Equiv Zn2+ 3 Equiv Cd2+ 3 Equiv Hg2+ 3 Equiv Pb2+ 3 Equiv Mn2+ 3 Equiv Fe2+ 3 Equiv Co2+ 3 Equiv Ni2+ 3 Equiv Cu2+
HN O
N
H O
+
Zn2+ piperazine
[Zn6(IDC)4(OH)2(Hprz)2]13H2O
OO H
benzene
THF acetone xylene ethanol
toluene
water as-synthesized
simulated
10
20
30
40
50
2Theta (deg)
simulated