1 three-dimensional porous coordination polymer functionalized with amide groups based on tridentate...
TRANSCRIPT
1
Three-Dimensional Porous Coordination Polymer Functionalized with Amide Groups Based on Tridentate Ligand: S
elective Sorption and Catalysis
Shinpei Hasegawa, Satoshi Horike, Ryotaro Matsuda, Shuhei Furukawa, Katsunori Mochizuki, Yoshinori Kinoshita, and Susumu
Kitagawa*
J. Am. Chem. Soc. 2007, 129, 2607-2614
演講者:江柏誼
2
Porous Coordination Polymers (PCPs)
porous coordination polymer Susumu Kitagawa. Natue. 2006, 441, 584-585
[{RhII2(bza)4(2-mpyz)}n]
O
-O
benzoate(bza)
N
N
2-methylpyrazine(2-mpyz)
3
PCPs have Characteristics
(1) well-ordered porous structures
(2) flexible and dynamic behaviors in response to guest molecules
(3) designable channel surface functionalities
4
Strategies to Functionalize Channel Surfaces
I 、 immobilization of coordinatively unsaturated| (Open) Metal Sites (OMS)
Noro, S.; Kitagawa, S.; Yamashita, M.; Wada, T. Chem. Commun. 2002, 222-223.
{[ZnCu(2,4-pydca)2(H2O)3
(DMF)]·DMF}n
N
O
O-
O
-O
pyridine-2,4-dicarboxylate(2,4-pydca)
5
Strategies to Functionalize Channel Surfaces (continued)
II 、 introduction of organic groups to provide guest-accessible Functional Organic Sites (FOS)
Kitaura, R.; Fujimoto, K.; Noro, S.; Kondo, M.; Kitagawa, S.; Angew. Chem. Int. Ed. 2002, 41, 133-135.
[{[Cu2(pzdc)2(dpyg)] ‧8H2O}n]1,2-dipyridylglycol (dpyg)
coordination site
guest interaction site
N
NO
-O
OO-
pyrazine-2,3-dicarboxylate(pzdc)
6
FOS have Advantages
• Base-type catalyst is easy to create 。
• There are a variety of organic functional groups that can serve as active base sites 。
• A new types of catalysts constructed from metal-organic frameworks 。
7
4-Btapa
1,3,5-Benzene Tricarboxylic AcidTris[N-(4-pyridyl)amide]
(4-btapa)
-NH electron acceptor
-C=O electron donor
8
Synthesis of 4-Btapa
NH2N
4-aminopyridine
1.triethylamine, THF
2.dropwise addation
1,3,5-benzene tricarboxytrichloride
, THF, 0oC3.triethylamine, THF, stir 7 hour
O O
NH
O NH
NH
NN
N
4-btapa4.filtration and washed with THF
N
triethylamine
(1,3,5-benzene tricarboxytrichloride)
O
O
O
ClCl
ClTrimesoyl Chloride
(81%)
yellowish whitepowder
9
Cd(NO3)2¡E4H2O
1. DMF2. 4-btapa/DMF
3. stir 3.5 hour4. filtration,washed with DMF
{[Cd(4-btapa)2(NO3)2]¡E6H2O¡E2DMF}n
1aunder vacuum for 7.5 hour at 140oC
{[Cd(4-btapa)2]¡E2NO3}n
1bon the methanol vapor for 30 hour
{[Cd(4-btapa)2(NO3)2]¡E6MeOH¡EyH2O}n
Synthesis of 1a, 1b, and 1c
yellowish whitepowder
(1a)
(1b)
(1c)colorless
(93%)
10
ORTEP Drawing of 1a
Solid-state 113Cd CPMAS NMR spectrum of 1a
11
Table 1. Selected Bond Distances (Å) and Angles (deg)
for {[Cd(4-btapa)2(NO3)2]·6H2O·2DMF}n (1a) Cd (1)-N1 2.372 (7) Cd1-N11 2.372 (8)
Cd1-N12 2.372 (8) Cd1-N13 2.372 (8)
Cd1-N14 2.372 (8) Cd1-N15 2.372 (7)
N11-Cd1-N1 90.8 (3) N12-Cd1-N1 90.8 (3)
N13-Cd1-N1 N14-Cd1-N1 89.2 (3)
N15-Cd1-N1 N12-Cd1-N11 90.8 (3)
N13-Cd1-N11 89.2 (3) N44-Cd1-N41 89.2 (3)
N15-Cd1-N11 180.0 (4) N13-Cd1-N12 89.2 (3)
N14-Cd1-N12 180.0 (4) N15-Cd1-N12 89.2 (3)
N14-Cd1-N13 90.8 (3) N15-Cd1-N13 90.8 (3)
N15-Cd1-N14 90.8 (3)
12
Crystal Structure of 1a
13
Two-Fold Interpenetrating 3-D Crystal Structure of 1a to Form Three-Dimension
4.7 X 7.3 Å2
14
Crystal Structure of 1a to Form Another Type of Zigzag Channels
3.3 X 3.6 Å2
15
The Amide Groups on the Channel Surface of 1a
Cd
O
N
16
Thermogravimetric Analyses of 1a and 1c
at a heating rate of 10 °C min-1 under N2
Amount of guests in figures is based on one 4-btapa ligand of each compound.
{[Cd(4-btapa)2(NO3)2] ‧6H2
O‧2DMF}n
{[Cd(4-btapa)2(NO3)2] ‧6MeOH‧yH2O}n
17
XRPD Patterns of 1a and 1b
1a simulation based on the single-crystal structure
the as-synthesized 1a
the desolvated compound 1b
compound 1c obtained by exposing 1b to methanol vapor for 30 h.
18
XRPD Patterns for Desolvated Compound 1b Immersed in Slovent
19
The Adsorption and Desorption Isotherms of 1b for Methanol
adsorption
desorption
P0 is the saturated vapor pressure, 102.3 kPa, of N2 (77 K), and16.94 kPa, of methanol (298 K).
hysteresis loop
20
1H NMR (DMSO-d6) Spectra of 1a that Adsorbed Each Guest Molecule
malononitrile
ethyl cyanoacetate
cyanoacetic acid tert-butyl ester
2.9
0.7
0.6
21
IR Spectra in the Region of C≡N Stretching Vibration Bands
υsCN―υas
CN at 2180 and 2200 cm-1
malononitrile
1a containing malononitrile
1a containing ethyl cyanoacetate
1a containing cyano-acetic acid tert-butyl ester
22
Table 2. Knoevenagel Condensation Reaction of Benzla
ldehyde with Substrates, Catalyzed by 1a
23
Conversion (%) vs Time (h) for Knoevenagel Condensation Reactions
24
Conclusion
• This work describes the construction of a 3D PCP containing guest-accessible amide groups and characterizes the selective inclusion of guest molecules with the structural transformation of the host 。
• We observed selective guest inclusion via the hydrogen bond, which is based on not only the size and shape of the incoming guest but also its affinity for the amide group.
25
• As a result, the Knoevenagel condensation reaction, which is a well-known base-catalyzed model reaction, was selectively promoted in good yield 。
• This research is particularly relevant in the context of porous solid-state chemistry in the generation of new materials with FOS 。