Journal of the American Chemical Society
Page 4 of 6
Å, as estimated by PM3 calculations). For SIOC-COF-2, BET
sophisticated topologies from relatively simple building
surface area of 46.13 m2/g (Figure S20) and total pore volume
(evaluated at P/P0 =0.99) of 0.09 cm3/g were obtained from
its nitrogen sorption isotherm. Pore size distribution analysis
revealed three main distributions around 11.3, 13.8 and 32.7 Å
(Figure 4f). These values are consistent with the simulated
pore distributions which were predicted to be 11.2, 13.6 and
38.9 Å. The results from pore size distribution analyses, to-
gether with the PXRD investigation, corroborated the obten-
tion of triple-pore COFs from the three-component co-
polymerization. It should be noted that BET surface areas of
TPDA-based COFs are quite low and the reason is currently
unclear. However, it detracts nothing from the determina-
blocks. Its potential to construct more complicated COFs is
currently under investigation in our laboratory.
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ASSOCIATED CONTENT
Supporting Information
Procedure for the preparation of the polymers, FT-IR spectra,
solid-state 13C CP-MAS NMR spectra, BET plots, TGA traces,
and SEM images. This material is available free of charge via
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AUTHOR INFORMATION
Corresponding Author
tions of the crystal structures of the COFs.
Notes
The authors declare no competing financial interests.
3000
b
a
31.8
Å
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8
12.7
Å
adsorption
desorption
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ACKNOWLEDGMENT
We thank the National Natural Science Foundation of China
(Nos. 21172249, 21472225) for financial support.
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6
adsorption
desorption
4
30.6
Å
2
7.3
Å
0
0
0.0
0.2
0.4
0.6
0.8
10
100
Relative Pressure (P/P )
0
Pore Width (Angstrom)
e
500
3.0
f
adsorption
desorption
13.8
Å
2.5
2.0
1.5
1.0
0.5
0.0
400
300
200
100
0
11.3
Å
32.7
Å
0.0
0.2
0.4
0.6
0.8
10
100
Pore Width (Angstrom)
Relative Pressure (P/P )
0
Figure 4. N2 adsorption-desorption isotherms (77 K) of (a)
COF-BPDA, (c) SIOC-COF-1 and (e) SIOC-COF-2, and pore
size distribution profiles of (b) COF-BPDA, (d) SIOC-COF-1
and (f) SIOC-COF-2.
In conclusion, COFs which bear three different kinds of
ordered pores with controllable sizes have been constructed
through heterostructural mixed linker strategy. While the
condensation of a D2h symmetric tetraamine and a C2 sym-
metric dialdehyde gave rise to a dual-pore COF containing
two different kinds of pores (triangular micropores and hex-
agonal mesopores), the copolymerization of a D2h symmetric
tetraamine and two C2 symmetric dialdehydes of different
lengths produced a triple-pore COF in the unit of which an
inequilateral hexagonal mesopore is alternatingly surround-
ed by three small triangular micropores and three big trian-
gular micropores. These COFs represent a new topology with
unprecedented hierarchy and structural complexity. This
work for the first time demonstrates that heterostructural
mixed linker strategy can also be applicable to construction
of COFs. It may open up a new way to fabricate COFs with
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