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

Outline

• Introduction• Experimental• Result• Application• Conclusion

Introduction

What is conjugated microporous polymer?

• Conjugated microporous polymers (CMPs) are a class of organic porous polymers that combine π-conjugated skeletons with permanent nanopores.

Encapsulation

Light Emitting

CMPsChemical Sensors

Gas Storage

Experimental

Advantages of conjugated microporous polymer

• High flexibility for the molecular design of conjugated skeletons and nanopores.

CMPsMolecular Design

Structural Control

Reaction Exploration

Applications

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

Building block

Fig. 2 Schematic representation of reactions for the synthesis of CMPs.

Construct the conjugated skeleton

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

Result

Monomer length and geometry

Fig. 3 Schematic representation of phenylethynylene-based CMPs.

CMPs Surface area(m2/g)

Pore volume(cm3/g)

CMP-0 1018 0.38

CMP-1 834 0.33

CMP-2 634 0.25

CMP-3 522 0.18

CMP-5 512 0.16

Monomer length and geometry

Fig. 4 Schematic representation of the synthesis of spirobifluorene-based CMPs using linkers of different geometries.

CMPs Surface area(m2/g)

YSN 1275

YSN-Para 887

YSN-Meta 361

YSN-Ortho 5

Statistical copolymerization scheme

Fig. 5 Schematic representation of the synthesis of CMPs using two linkerunits (DIB and DIBP) in different molar ratios

CMPs Surface area(m2/g)

Pore volume(cm3/g)

CNP-1 856 0.32

CNP-2 775 0.31

CNP-3 759 0.30

CNP-4 749 0.29

CNP-5 722 0.29

CNP-6 643 0.25

Reaction conditions

• Reaction media(solvent) type• Catalyst ratio• Reaction temperature• Reaction time

Application

Gas adsorption and storage

Fig. 6 Schematic representation of the synthesis of poly(phenylene butadiynylene)-based CMPs.

Physical adsorption

Gas adsorption and storage

Fig. 7 Schematic representation of the synthesis of polyphenylethynylenebasedCMPs having different functional groups on the pore wall.

Chemical adsorption

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)

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))

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 agents Light Emitting

Sensor device

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.

Conclusion

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 m2/g

remains a considerable challenge.

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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Thanks for your attention!