Constructing Crystalline Covalent Organic Frameworks from Chiral Building Blocks

Article abstract of DOI:10.1021/jacs.6b07516

Covalent organic frameworks (COFs) represent a new type of crystalline porous materials that are covalently assembled from organic building blocks. Construction of functional COFs is, however, a difficult task because it has to meet simultaneously the requirements for crystallinity and functionality. We report herein a facile strategy for the direct construction of chiral-functionalized COFs from chiral building blocks. The key design is to use the rigid scaffold 4,4′-(1H-benzo[d]imidazole-4,7-diyl)dianiline (2) for attaching a variety of chiral moieties. As a first example, the chiral pyrrolidine-embedded building block (S)-4,4′-(2-(pyrrolidin-2-yl)-1H-benzo[d]imidazole-4,7-diyl)dianiline (3) was accordingly synthesized and applied for the successful construction of two chiral COFs, LZU-72 and LZU-76. Our experimental results further showed that these chiral COFs are structurally robust and highly active as heterogeneous organocatalysts.

Full text of DOI:10.1021/jacs.6b07516

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Communication
Constructing Crystalline Covalent Organic
Frameworks from Chiral Building Blocks
Hai-Sen Xu, San-Yuan Ding, Wan-Kai An, Han Wu, and Wei Wang
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 01 Sep 2016
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Constructing Crystalline Covalent Organic Frameworks from
Chiral Building Blocks
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HaiꢀSen Xu,† SanꢀYuan Ding,*,† WanꢀKai An,† Han Wu,† and Wei Wang*,†,‡
†State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou
University, Lanzhou, Gansu 730000, China
‡Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300071, China
Supporting Information Placeholder
ABSTRACT: Covalent organic frameworks (COFs)
represent a new type of crystalline porous materials which
are covalently assembled from organic building blocks.
Construction of functional COFs is however a difficult task
because it has to simultaneously meet the requirements for
crystallinity and functionality. We report herein a facile
strategy for the direct construction of chiralꢀfunctionalized
COFs from chiral building blocks. The key design is to use
the
rigid
scaffold
4,4'ꢀ(1Hꢀbenzo[d]imidazoleꢀ4,7ꢀ
diyl)dianiline (2) for attaching a variety of chiral moieties.
As a first example, the chiral pyrrolidineꢀembedded building
block (S)ꢀ4,4'ꢀ(2ꢀ(pyrrolidinꢀ2ꢀyl)ꢀ1Hꢀbenzo[d]imidazoleꢀ
4,7ꢀdiyl)dianiline (3) was accordingly synthesized and
applied for the successful construction of two chiral COFs,
LZU-72 and LZU-76. Our experimental results further
showed that these chiral COFs are structurally robust and
highly active as heterogeneous organocatalysts.
Figure 1. General strategies for constructing chiral porous
materials: a) postꢀmodification of achiral porous supports
with chiral moieties, and, b) direct construction from chiral
building blocks. The latter strategy intrinsically guarantees
the homogeneous dispersion of chiral functionalities with
the highest content.
Introduced by the seminal work of Yaghi,12 covalent
organic frameworks (COFs) represent an emerging class of
crystalline porous materials which are covalently
constructed from organic components.13 In comparison with
amorphous polymers, COFs possess wellꢀdefined crystalline
structures with regular pore channels, which could
potentially work as "organic zeolite".14 However, functional
COFs remain difficult to synthesize because crystallinity,
porosity, and functionality have to be simultaneously taken
into account. In this context, construction of chiral COFs is,
if not possible, extremely challenging. The key bottleneck is
the intrinsic mismatch between the symmetry for crystalline
structure and asymmetry for chiral functionality. Very
recently, Jiang pioneered the research by a successful postꢀ
modification (Figure 1a) of achiral COFs with chiral
moieties.3f,g However, the direct construction of chiral COFs
from chiral building blocks (Figure 1b) remains unexploited.
Chiral compounds are of great importance in
pharmaceutics, agriculture, and other chemical industries.1
In recent years, chiral materials have attracted intensive
research interest because they combine the advantages of
chiral functionality and facile reusability.2 Particularly,
chiral porous materials have emerged as a new research
area towards the promising applications in catalysis,3
separation,4 and recognition.5 To date, most of the chiral
porous materials are synthesized via postꢀmodification of
achiral porous supports with chiral moieties (Figure 1a).6
This strategy, however, leads to uneven distribution and less
loading of chiral functionalities.7 In this context, the direct
construction of porous materials from chiral building blocks
represents an alternative but challenging approach (Figure
1b).3b,8 In 2009, we initiated a project focusing on the
"bottomꢀup" construction of porous organic materials.9 Two
chiral porous polymers (CPP), JHꢀCPP and TADDOLꢀCPP
were accordingly synthesized from chiral building blocks.10
Due to fast and irreversible formation of strong covalent
bonds, these CPP materials were unfortunately amorphous
in nature. Accordingly, the reproducibility of their synthesis
and function was less controlled.11 In this regard, crystalline
porous materials with wellꢀdefined structures are highly
desired for chiral applications. In this contribution, we
achieved the direct construction of crystalline covalent
organic frameworks from chiral building blocks.
We tackled this challenge by the judicious design of chiral
building blocks (Figure 2). Firstly, the linearꢀstructured
4,4'ꢀdiaminoꢀpꢀterphenyl (1) was chosen as the basic
backbone because the rigid and symmetric terphenyl group
is ideal for constructing COFs with large open channels.15
Base on this backbone, the imidazole group16 was
incorporated into the middle phenyl ring to afford the
scaffold 4,4'ꢀ(1Hꢀbenzo[d]imidazoleꢀ4,7ꢀdiyl)dianiline (2).
Note that the scaffold 2 is very versatile for attaching a
variety of functional moieties.17 For example, the chiral
pyrrolidine moiety could be further incorporated to afford
the chiral building block (S)ꢀ4,4'ꢀ(2ꢀ(pyrrolidinꢀ2ꢀyl)ꢀ1Hꢀ
benzo[d]imidazoleꢀ4,7ꢀdiyl)dianiline (3). It is worth to
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mention that, 3 is very facile to synthesize with 99%
condensation of NꢀBocꢀprotected 318 with
4 or triꢀ
1
2
3
4
enantiomeric excess (ee) from commercially available Nꢀ
BocꢀLꢀproline (see Supporting Information for details) and,
it perfectly integrates the asymmetric chirality with the
symmetric backbone.
formylphloroglucinol (5), respectively (see Supporting
Information for details). The synthetic condition is quite
mild and the synthetic route is well reproducible. Therefore,
these chiral crystalline COFs could be easily synthesized for
chiral applications.
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Figure 2. Our design for the chiral building block 3, which
integrates the rigid and symmetric backbone with the chiꢀ
ralꢀpyrrolidine moiety.
Figure 4. 13C CP/MAS NMR spectra of LZU-72 (a) and
LZU-76 (b). The asterisks denote the spinning sidebands.
Assignments of 13C chemical shifts were indicated in the
chemical structures of LZU-72 and LZU-76, respectively.
The atomicꢀlevel construction of LZU-72 and LZU-76
was assessed by Fourier transform infrared (FTꢀIR) and
solidꢀstate NMR spectroscopy. The FTꢀIR spectrum of
LZU-72 showed an intense –C=N– stretch at 1621 cmꢀ1,
indicating the formation of imine bonds (Figure S16). LZU-
76 displayed a strong –C–N– stretch at 1256 cmꢀ1 and a –
C=C– stretch at 1592 cmꢀ1, which are characteristic of
β−ketoenamine linkages (Figure S39).14d,19 More detailed
information was given by 13C crossꢀpolarization magicꢀangle
spinning (CP/MAS) NMR analysis (Figure 4). The 13C
CP/MAS NMR spectra of both COFs exhibited signals at 25,
31, 47, and 55 ppm, which are assigned to the chiral
pyrrolidine moieties. The detailed assignments of 13C
chemical shifts were depicted in Figure 4.
The crystalline structures of LZU-72 and LZU-76 were
determined by powder Xꢀray diffraction (PXRD) analysis
with Cu Kα radiaction. The observed PXRD patterns of
LZU-72 (Figure 5a, black) showed an intense peak with the
d spacing of 32.42 Å and two other peaks with d spacings of
16.21 and 10.81 Å, which correspond to the 100, 200, and
300 reflections, respectively. Similarly, the observed PXRD
patterns of LZU-76 (Figure 5b, black) exhibited three peaks
with the
d spacings of 32.40, 16.20, and 10.80 Å,
respectively. Structural modeling was then conducted with
the software of Materials Studio (ver. 7.0). The Pawleyꢀ
refined PXRD profiles matched the experimental PXRD
patterns very well (Rwp of 6.73% and Rp = 4.86% for LZU-
72; Rwp of 4.59% and Rp of 2.90% for LZU-76).
Comparison of the experimental and the calculated PXRD
patterns (Figures S37 and S56) indicated that the stacking
structures of LZU-72 and LZU-76 were both the eclipsed
arrangements. Notably, both COFs possess the chiral space
group of P3, which should be originated from the existence
of chiral building blocks. In addition, the transmission
electron micrographs (TEM) image (Figure S36) showed
longꢀordered channels in LZU-72 with a distinct pore size
Figure 3. Schematic representation for the direct
construction of chiral COFs, LZU-72 and LZU-76.
As a primary test, we used the achiral diamine 2 and
1,3,5ꢀtriformylbenzene (4) to explore the possibility of synꢀ
thesizing crystalline COFs. To our delight,
a highlyꢀ
crystalline COF, LZU-70, was successfully obtained with
permanent porosity (see Supporting Information for
details). It therefore encouraged us to construct chiral COFs
directly from the chiral building block 3 under similar
conditions. As shown in Figure 3, two chiral COFs, LZU-72
and LZU-76, were eventually synthesized from the direct
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of 2.0 nm. Meanwhile, the scanning electron microscopy
Table 1. Catalytic Activity Test of LZU-76 in
Asymmetric Aldol Reactiona
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2
3
(SEM) images revealed that LZU-72 exhibited a sphere
morphology (Figure 5c), while LZU-76 showed a threadꢀ
like morphology (Figure 5d).
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Time
[h]
Yield
[%]b
Entry
Ar
Catalyst
LZU-76
LZU-76
LZU-76
LZU-76
e.r.c
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2
3
4
5
6
4ꢀNO2Ph
2ꢀNO2Ph
4ꢀCNPh
4ꢀBrPh
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18
48
96
80
6
73
84
71
94.0:6.0
93.7:6.3
93.5:6.5
88.4:11.6
91.4:8.6
93.1:6.9
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2ꢀnaphthyl LZU-76
4ꢀNO2Ph
DPBIPd
aGeneral conditions: aromatic aldehydes (0.20 mmol),
LZU-76 (0.06 mmol), trifluoroacetic acid (TFA) (0.06
mmol), and acetone (1.0 mL). bIsolated yield. cEnantiomeric
ratios (e.r.) were determined by chiral HPLC. dFor the
purpose of comparison, (S)ꢀ4,7ꢀdiphenylꢀ2ꢀ(pyrrolidinꢀ2ꢀ
yl)ꢀ1Hꢀbenzo[d] imidazole (DPBIP) was synthesized as the
homogeneous counterpart of LZU-76.
The catalytic activity of LZU-76 was evaluated in the
asymmetric aldol reaction, which is one of the most
important routes for asymmetric C–C bond formation.23 As
shown in Table 1, catalyzed by LZU-76, the reaction
afforded the desired aldol products with excellent
enantioselectivity (88.4:11.6ꢀ94.0:6.0 e.r., entries 1ꢀ5). For
the purpose of comparison, a model catalyst, (S)ꢀ4,7ꢀ
diphenylꢀ2ꢀ(pyrrolidinꢀ2ꢀyl)ꢀ1Hꢀbenzo[d]imidazole
(DPBIP) was synthesized as the homogeneous counterpart
of LZU-76 and its catalytic activity was investigated under
the same conditions. The result indicates that LZU-76
(entry 1) showed comparable enantioselectivity to DPBIP
(entry 6). In addition, LZU-76 could be easily recovered by
centrifugation and reused at least for 3 times without loss of
enantioselectivity (Table S4). The PXRD patterns (Figure
S57) and 13C CP/MAS NMR spectra (Figure S58) of the
recycled LZU-76 demonstrated that the crystallinity and
covalentꢀbonding were maintained.
Figure 5. Experimental (black), Pawley refined (orange),
and simulated (blue) PXRD patterns of LZU-72 (a) and
LZU-76 (b). The difference plots between the experimental
and the refined PXRD patterns are presented in green. Inꢀ
sets: The extended structures based on the eclipsed arꢀ
rangements. C, grey; O, red; N, blue. H atoms are omitted
for clarity. SEM images of LZU-72 (c) and LZU-76 (d).
The permanent porosity of LZU-72 and LZU-76 was
confirmed by nitrogen adsorptionꢀdesorption experiments
at 77 K (Figures S25 and S48). The BrunauerꢀEmmettꢀTeller
(BET) surface areas of LZU-72 (Figure S26) and LZU-76
(Figure S49) were calculated to be 1114 and 758 m2 gꢀ1,
respectively. The difference in the experimental BET surface
areas of LZU-72 and LZU-76 could be attributed to the
different crystallinity.20 Meanwhile, the theoretical BET
surface areas were calculated as 1521 m2 gꢀ1 for LZU-72
(Figure S32) and 1189 m2 gꢀ1 for LZU-76 (Figure S53), reꢀ
spectively. These theoretical values are higher than the exꢀ
perimental values, the case of which was also previously
reported for other 2D COFs.21 The pore volumes were
evaluated (at P/P0 = 0.99) to be 0.98 cm3 gꢀ1 for LZU-72
and 0.66 cm3 gꢀ1 for LZU-76. Calculated by nonlocal density
functional theory (NLDFT) method, both COFs exhibited a
narrow pore size distribution between 1.2 and 2.2 nm
(Figures S28 and S51). The difference in the pore size data
derived from the model structure and gas adsorption isoꢀ
therms may be attributed to the microcrystalline nature of
the synthesized COFs.14d,22
In conclusion, we develop herein
a straightforward
strategy for constructing chiral COFs directly from chiral
building blocks. The key design for the functional building
blocks is the use of rigid 2 as the scaffold for attaching the
chiral moieties. As a first example, two chiral COFs, LZU-
72 and LZU-76, were successfully constructed from the
chiralꢀpyrrolidineꢀcontaining building block 3. Given that
the versatile scaffold 2 could attach different chiral moieties,
various chiral COFs are expected to facilely construct via
this strategy. It, therefore, paves a new way for the
construction of functional COFs for high valueꢀadded
applications.
ASSOCIATED CONTENT
Supporting Information
One of the most valueꢀadd applications of chiral materials
is as heterogeneous asymmetric catalysts. In this aspect, the
straight channels within these two crystalline COFs could
provide efficient access to the chiralꢀpyrrolidine sites and
thus facilitate the transport of reactants and products. In
particular, LZU-76 is more stable under acidic conditions
(Figure S42) due to the robust β−ketoenamine linkages.14d
Accordingly, we chose LZU-76 to test its catalytic activity.
Detailed synthetic procedures, FTꢀIR spectra, 13C CP/MAS
NMR spectra, TGA traces, gas adsorption, SEM images,
TEM images, PXRD patterns, modeling details and atomic
coordinates, catalytic activity test, liquid NMR spectra, and
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AUTHOR INFORMATION
Corresponding Author
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wang_wei@lzu.edu.cn; dingsy@lzu.edu.cn
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ACKNOWLEDGMENT
This work was financially supported by the National Natural
Science Foundation of China (Nos. 21425206 and
21502081).
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