1 Three-Dimensional Porous Coordination Poly mer Functionalized with Amide Groups Based on Tridentate Ligand: Selective Sorption a nd Catalysis Shinpei Hasegawa, Satoshi Horike, Ryotaro M atsuda, Shuhei Furukawa, Katsunori Mochizuk i, Yoshinori Kinoshita, and Susumu Kitagawa * J. Am. Chem. Soc. 2007, 129, 2607-2614 演演演 演演演 :
25
Embed
1 Three-Dimensional Porous Coordination Polymer Functionalized with Amide Groups Based on Tridentate Ligand: Selective Sorption and Catalysis Shinpei Hasegawa,
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Transcript
1
Three-Dimensional Porous Coordination Polymer Functionalized with Amide Groups Based on Tridentate Ligand: S
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 。