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