Porous Coordination Polymers (PCPs)

1. Three-Dimensional Porous Coordination Polymer Functionalized with Amide Groups Based on Tridentate Ligand: Selective 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) [{RhII2(bza)4(2-mpyz)}n] Susumu Kitagawa. Natue.2006, 441, 584-585 porous coordination polymer

3. PCPs have Characteristics • well-ordered porous structures • flexible and dynamic behaviors in response to guest molecules • designable channel surface functionalities

4. Strategies to Functionalize Channel Surfaces I、immobilization of coordinatively unsaturated| (Open) Metal Sites (OMS) {[ZnCu(2,4-pydca)2(H2O)3 (DMF)]·DMF}n Noro, S.; Kitagawa, S.; Yamashita, M.; Wada, T. Chem. Commun. 2002, 222-223.

5. coordination site guest interaction site 1,2-dipyridylglycol (dpyg) [{[Cu2(pzdc)2(dpyg)] ‧8H2O}n] 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.

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. -NH electron acceptor -C=O electron donor 1,3,5-Benzene Tricarboxylic Acid Tris[N-(4-pyridyl)amide] (4-btapa) 4-Btapa

8. Synthesis of 4-Btapa (81%) yellowish white powder

9. yellowish white powder Synthesis of 1a, 1b, and 1c (1a) (93%) (1b) (1c) colorless

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)

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 N O Cd

16. Thermogravimetric Analyses of 1a and 1c {[Cd(4-btapa)2(NO3)2] ‧6H2O‧2DMF}n {[Cd(4-btapa)2(NO3)2] ‧6MeOH‧yH2O}n 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.

17. XRPD Patterns of 1a and 1b compound 1c obtained by exposing 1b to methanol vapor for 30 h. the desolvated compound 1b the as-synthesized 1a 1a simulation based on the single-crystal structure

18. XRPD Patterns for Desolvated Compound 1b Immersed in Slovent

19. The Adsorption and Desorption Isotherms of 1b for Methanol desorption hysteresis loop adsorption P0 is the saturated vapor pressure, 102.3 kPa, of N2 (77 K), and 16.94 kPa, of methanol (298 K).

20. 2.9 0.7 0.6 1H NMR (DMSO-d6) Spectra of 1a that Adsorbed Each Guest Molecule malononitrile ethyl cyanoacetate cyanoacetic acid tert-butyl ester

21. IR Spectra in the Region of C≡N Stretching Vibration Bands υsCN―υasCN 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 Benzlaldehyde 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。