1. Conjugated microporous polymers: design, synthesis and application Advisor: Professor Guey-Sheng Liou Reporter: Chin-Yen Chou 2013/11/15 Yanhong Xu, Shangbin Jin, Hong Xu, Atsushi Nagai, Donglin Jiang Chem. Soc. Rev., 2013,42, 8012-8031

2. Outline Introduction Experimental Result Application Conclusion

3. Introduction

4. What is conjugated microporous polymer? Conjugated microporous polymers (CMPs) are a class of organic porous polymers that combine π-conjugated skeletons with permanent nanopores.

5. Encapsulation Light Emitting CMPs Chemical Sensors Gas Storage

6. Experimental

7. Advantages of conjugated microporous polymer High flexibility for the molecular design of conjugated skeletons and nanopores. CMPs Molecular Design Structural Control Reaction Exploration Applications

8. Fig.1 Schematic representation of the structures of building blocks with different geometries, sizes and reactive groups for the synthesis of CMPs. Building block

9. Fig. 2 Schematic representation of reactions for the synthesis of CMPs. Construct the conjugated skeleton

10. Design Concept 1.Geometric requirements 2.Diversity of reactive groups Control by tunning the monomer length and geometry Control by using a statistical copolymerization scheme Control by tunning reaction conditions

11. Result

12. Monomer length and geometry Fig. 3 Schematic representation of phenylethynylene- based CMPs. CMPsSurface area (m 2 /g) Pore volume (cm 3 /g) CMP-010180.38 CMP-18340.33 CMP-26340.25 CMP-35220.18 CMP-55120.16

13. Monomer length and geometry Fig. 4 Schematic representation of the synthesis of spirobifluorene-based CMPs using linkers of different geometries. CMPsSurface area (m 2 /g) YSN1275 YSN-Para887 YSN-Meta361 YSN-Ortho5

14. Statistical copolymerization scheme Fig. 5 Schematic representation of the synthesis of CMPs using two linker units (DIB and DIBP) in different molar ratios CMPsSurface area (m 2 /g) Pore volume (cm 3 /g) CNP-18560.32 CNP-27750.31 CNP-37590.30 CNP-47490.29 CNP-57220.29 CNP-66430.25

15. Reaction conditions Reaction media(solvent) type Catalyst ratio Reaction temperature Reaction time

16. Application

17. Gas adsorption and storage Fig. 6 Schematic representation of the synthesis of poly(phenylene butadiynylene)- based CMPs. Physical adsorption

18. Gas adsorption and storage Fig. 7 Schematic representation of the synthesis of polyphenylethynylenebased CMPs having different functional groups on the pore wall. Chemical adsorption

19. Encapsulation Fig. 8 (a)Schematic representation of the synthesis of porphyrin-based CMPs. (b) Photo of a water droplet, and (c) photo of a salad oil droplet on a tablet of the PCPF-1 sample. (a) (b) (c)

20. Light emitters Fig9. Schematic representation of the synthesis of pyrene-based CMPs and the photographs of suspensions in THF (under irradiation with UV light (365 nm))

21. Chemical sensors Fig. 10 Schematic Representations of (A) the Carbazole-based CMP (TCB- CMP) and the Linear Polymer Analogue CB-LP and (B) the Elementary Pore Skeleton of TCB-CMP Chemical agentsLight Emitting Sensor device

22. Chemical sensors Figure 11. (A) Electronic absorption and fluorescence spectra of TCB-CMP (red) and CB-LP (black) powders. (B) Images of TCB-CMP and CB-LP (in PEG and (right) under a UV lamp.

23. Conclusion

24. CMPs are a unique class of polymers that inherently combine π conjugation with porosity. The diversity of chemical reactions, the availability of building blocks and the variety of synthetic methods give rise to the generation of CMPs with different structures and functions. As a platform for designing porous materials, CMPs provide a powerful means for tuning the porosity, pore environment and functionality. Achieving high surface areas over 3000 m 2 /g remains a considerable challenge.

25. As a platform for designing π-conjugated materials, CMPs are useful for developing 3D networks that allow exciton migration and carrier transport. The synthesis of low-bandgap CMPs is of particular importance but remains difficult. In this sense, systematic investigations are essential for clarifying the structure–property correlation, which remains unclear in many CMPs. Similarly, the charge dynamics in these 3D CMP networks is another important aspect to be explored.

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27. Thanks for your attention!