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Cage Based Crystalline Covalent Organic Frameworks Jian-Xin Ma, Jian Li, Yi-Fan Chen, Rui Ning, Yu-Fei Ao, JunMin Liu, Junliang Sun, De-Xian Wang, and Qi-Qiang Wang J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b00665 • Publication Date (Web): 18 Feb 2019 Downloaded from http://pubs.acs.org on February 18, 2019

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Journal of the American Chemical Society

Cage Based Crystalline Covalent Organic Frameworks Jian-Xin Ma,†,‖,⊥ Jian Li,‡,⊥ Yi-Fan Chen,§ Rui Ning,†,‖ Yu-Fei Ao,† Jun-Min Liu,§ Junliang Sun,‡ DeXian Wang,†,‖ and Qi-Qiang Wang*,†,‖ †Beijing

National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China ‡Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China §School

of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510275, China

‖University

of Chinese Academy of Sciences, Beijing 100049, China

Supporting Information Placeholder ABSTRACT: The first two cage based crystalline covalent organic frameworks, cage-COF-1 and cage-COF-2, were constructed from a prism-like three-aldehyde-containing molecular cage. The cage contains two horizontal phloroglucinol and three vertical triazine moieties forming three identical Vshaped cavities. By reacting with p-phenylenediamine and 4,4'biphenyldiamine, the two cage-COFs were formed with a hexagonal skeleton and possess a unique structure. Due to the pillared cage nodes, the linkers are hanging with their -surfaces but not C-H sites exposed to the pore, and enjoy certain rotational dynamics as suggested by 13C CP/MAS NMR. The anti-direction of the diimine linkages leads to rippled layers which pack in unique ABC mode through alternate stacking of the cage twosided faces in both AB and AC layers. Such packing forms trigonal channels along c axis which are interconnected in ab plane due to the large open space created across the hanging linkers, resembling the porous characteristics of 3D COFs. The cageCOFs have a permanent porosity and can adsorb CO2 facilitated by the intrinsic cage cavities that serve as prime adsorption sites. The unprecedented cage-COFs not only merge the borderline of 2D and 3D COFs, but also bridge porous organic cages to extended crystalline organic frameworks.

Covalent organic frameworks (COFs) are emerging crystalline porous materials in which organic subunits are built into two- or three-dimensional architectures via strong covalent bonds.1,2 The well-defined structure, designable construction and tailored functionality have offered COFs great potential in diverse applications including gas adsorption,3 separation4 and catalysis.5 Since the seminal work of Yaghi and co-workers in 2005,1 this field has received rapid development and a large number of COFs have been constructed based on reticular chemistry.2 Commonly, the topology design is realized by use of planar and tetrahedral units as knots to connect with appropriate linkers to form 2D and 3D COFs respectively. So far the building units are limited to multi-substituted arenes and few macrocyclic skeletons.6-9 Meanwhile, discrete organic cages possessing intrinsic cavity and porosity have received great interests in past decades.10 The use of such cages as building units to construct extended networks, the cage-to-framework strategy, is particularly appealing. It could combine diverse properties in an emergent fashion, for example, to merge the molecular benefits of soluble cages and the robustness and durability of polymeric systems.11 This strategy

has been recently demonstrated in successful fabrication of cage based metal organic frameworks or supramolecular coordination frameworks,12 and organic cage frameworks.13 However, the cage based crystalline covalent organic frameworks – ‘cage-COFs’, to the best of our knowledge, have not been realized probably due to the chanlleges on structural design and control. Here, we report the successful design and construction of two examples of cageCOFs from a prism-like organic molecular cage for the first time. Recently we have synthesized a rigid, D3h-symmetric molecular cage consisting of two parallel phloroglucinol and three vertical chlorine-substituted triazine moieties.14 It possesses three electron-deficient V-shaped cavities, and can be an excellent platform for building sophisticated molecular architectures such as a discrete molecular barrel which strongly adsorbs CO2 facilitated by lone pair– interactions.15 Intrigued by the facile synthesis, the unique structure and cavity characteristics, we envisioned if this cage motif can be applied as a C3 building unit to construct cage-COFs, for example, by connection with C2 linkers (Figure 1). This would not only allow hierarchical construction of COFs from simple aromatic fragments but also render them intrinsic cage cavity. In contrast to traditional 2D COFs, the cage-COFs would have minimal interlayer -stacking (only cage twosided faces) and linkers hanging between pillared cage knots with their -surfaces but not C-H sites exposed to the pores. Furthermore, in such a way open interlayer space is created and would lead to interconnected pores, resembling pore characteristics of 3D COFs.16

Figure 1. Design of cage based covalent organic frameworks (cage-COFs).

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Scheme 1. Synthesis of Cage 1, 2, and Cage-COF-1, Cage-COF-2. CHO

+

3 N Cl

N N

N O

O OH

Cs2CO3

2 HO

OH

N

N

N O

N O

1

O

N N

N N O

Toluene, reflux, 12 h 88%

O

N O

Cl

O

N

O

O N N

NH2

N

N N O

DMF, rt , 2 h 53%

N O

N O

O N N

2

N

N

N NO O

NN O O NN O

N O

ON

N N

N

n

N

NO

O

O N N

N O

N N

O N O

ON

N N

N N O

N

N

N n

O

O

N O

NN O O NN

N n

N

NO

1

O

H 2N

NH2 n

n = 1, 2

ON

HOAc (3 M)

+

o-DCB (for n = 1) or 1,4-dioxane (for n = 2) 120 oC, 3 d

N

N N

O N O

NN O O NN

n = 1, Cage-COF-1 n = 2, Cage-COF-2

NN O O NN

O N O

N N

N

NO

ON N n

N N

nN NO NN O O NN

i

h g O N O

N N

fe

d c

ba

ON

jk lm

N

NO

N n

N N

O N O

NN O O NN ON N

N

To synthesize the cage precursor for COF construction, aldehyde groups were introduced onto the cage skeleton. The onepot reaction between 4-formylphenyl substituted dichlorotriazine and phloroglucinol gave the cage 1 in 53% yield (Scheme 1). The simple protocol and high efficiency allowed the easy multi-gram synthesis. To test the reactivity, the cage 1 was reacted with 3 eq. aniline and the imine cage 2 was readily formed in 88% yield. Crystal structures show the two cages possess a similar, prismlike skeleton with two phloroglucinol planes in parallel and three vertical triazines nearly 120o-branched, forming three V-shaped cavities (Figure 2). The height as determined by the distance of the two phloroglucinol planes is 4.5 Å and the openings of the three triazine V-clefts in large rim are in range of 8.9-9.6 Å. While the three formyl groups in 1 seem to orientate differently, the imine groups in 2 adopt the same orientation and lead to an overall C3-symmetry. Comparing to the most reported shapepersistent cages formed through dynamic covalent bonds, this cage skeleton represents a rare example formed by irreversible bonds.10 The prism-like structure and high stability enable the cage motif serving as a suitable cage-COF building unit.

powder by heating suspensions of 1 and the two diamines in odichlorobenzene or 1,4-dioxane in the presence of acetic acid (3 M), respectively (see Supporting Information). The synthesized COF materials are insoluble in water and common organic solvents. Thermogravimetric analysis (TGA) showed the materials are stable up to 400 °C (Figures S8-S9). Fourier transform infrared (FT-IR) spectrum showed the C=O stretching band at 1702 cm-1 is greatly attenuated comparing to the cage precursor, indicating that the free aldehydes were mostly consumed (Figure S2). The appeared C=N stretching band at 1622 cm-1 further confirmed the formation of imine linkages. The overall similarity of the spectra with that of the model imine cage 2 in skeleton vibration and fingerprint region suggested the cage skeleton remains intact. The atomic-level construction of the two cage-COFs and possible structural dynamics of the hanging linkers were further assessed by 13C cross-polarization magic-angle spinning (CP/MAS) NMR (Figure 3). By comparing with the spectra of cage 1 and 2, all the peaks can be assigned (Figure S3). The peak at ∼157 ppm is the characteristic signal for imine group (Ca). Interestingly, the signals for the edge carbon atoms on the pphenylene and 4,4'-biphenyl linkers (Ck for cage-COF-1, and Ck, Cl for cage-COF-2) are relatively sharp, implying that the hanging phenyl linkers experience significantly more motion. This was further suggested by T1 relaxation time measurements where these signals (and also the signals Cc, Cd) display much shorter T1 values than the other signals, even shorter than those in the amorphous samples (Figures S4-S7, Tables S2-S3).17 These outcomes taken together suggest that the hanging linkers could possess certain rotational dynamics due to the particular structure of the cage-based frameworks.

Figure 2. Crystal structures of (a) cage 1 and (b) cage 2. Hydrogen atoms and solvent molecules are omitted for clarity. Taking cage 1 as a C3-symmetric knot, p-phenylenediamine and 4,4'-biphenyldiamine were choosen as a C2 linker in order to produce a hexagonal COF skeleton (Scheme 1). The cage-COF-1 and cage-COF-2 were reproducibly synthesized as a yellow


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Journal of the American Chemical Society Figure 3. 13C CP/MAS NMR spectra of (a) Cage-COF-1 and (b) Cage-COF-2. For carbon assignments, see Scheme 1 and Figure S3. The asterisk denotes the unreacted aldehyde carbonyl signal. The crystallinity of the two cage-COFs were confirmed by powder X-ray diffraction (PXRD) analysis (Figure 4). The PXRD patterns exhibit intense peaks at 2 = 3.26, 5.62, 6.40 for cageCOF-1, and 2.77, 5.60, 6.33 for cage-COF-2, along with other minor peaks, indicating the long-range ordering in the frameworks. The possible extended structures were built by the Materials Studio suite of programs. Given that 2D cage fragments were expected to form, layered crystal structures were modeled, in which three distinct stacking possibilities were considered and optimized: i) AA stacking (space group P-3m1), ii) AB stacking (P-3m1), and iii) ABC stacking (each layer sequentially slipped along the diagonal of the hexagon, R-3m) (Figures 5 and S14-S15). The model with ABC stacking exhibits distinct diffraction pattern due to its R-lattice extinction, i.e. its (100) is absence due to the reflection condition for R-3m: hkl: -h + k + l = 3n. To our delight, for both of the two cage-COFs, the simulated PXRD pattern of the ABC stacking showed excellent agreement with the experimental profile in relative intensities and peak positions, while obvious mismatch stands for the other two models due to the presence of the strong (100) peak (Figure 4). Finally, the more accurate structure models with ABC packing were refined by the Rietveld refinement with soft restraints for the cage moiety and converged with acceptable low residuals Rp = 4.43%, Rwp = 5.92% (a = b = 56.74 Å, c = 17.40 Å) for cage-COF-1 and Rp = 2.96%, Rwp = 3.90% (a = b = 63.08 Å, c = 16.16 Å) for cage-COF-2. The layer structures of the two cage-COFs were also revealed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) where layered-sheet morphology was observed (Figures S10-S13).

a large interlayer open space is created between the hanging linkers (∼1 nm) and all trigonal channels are accordingly interconnected in ab plane, resembling the porous structure of 3D COFs.16 The hanging phenyl rings could enjoy some free rotation as suggested by 13C CP/MAS NMR studies (vide supra). Besides the major trigonal channel, a small open window (4.8 × 4.6 Å2) in ab plane arisen from the intrinsic cage cavities is also observed (Figure 5b).

Figure 5. Structural representations for (a) perspective, (b) side, (c) top, (d) pore view of cage-COF-1 and (e) pore view of cageCOF-2.

Figure 4. PXRD patterns of cage-COF-1 and cage-COF-2. (a, f) Observed (black, major reflections assigned) and refined modeling profile (red), (b, g) difference plot between observed and refined patterns. Simulated patterns for (c, h) ABC, (d, i) AA and (e, j) AB stacking models. The cage-COFs exhibit a unique structure in contrast to traditional 2D COFs. The hexagonal skeleton consists of six pillared cage knots and all vertical aromatic linkers. The preferred anti-direction of the diimine linkages leads to a rippled layer (Figures 5 and S16-S20). The layers pack in a most staggered mode through only -stacking of the cage phloroglucinol faces. The adoption of ABC other than AB packing model can maximize the stacking of all the phloroglucinol faces (in AB model only half of which can stack). The stacking distance is 3.4 Å in AB layer and 4.4 Å in AC layer. The rippled layer skeleton can prevent the sliding between layers. The unprecedent ABC packing forms trigonal channels along c axis in a diameter of about 1.2 and 1.4 nm for cage-COF-1 and cage-COF-2, respectively (Figures 5d, e). The channel surroundings are vertical -surfaces other than horizontal C-H sites as seen in common 2D COFs, which would lead to enhanced porosity and altered pore properties.18 Moreover,

The porosity of the cage-COFs were examined by nitrogen adsorption-desorption analysis at 77 K (Figure 6a). The BrunauerEmmett-Teller (BET) surface areas were found to be 1237 and 667 m2 g-1 for cage-COF-1 and cage-COF-2, respectively. Calculation using nonlocal density functional theory (NLDFT) revealed a narrow pore width distribution at ∼1.1 nm for both the cage-COFs, consistent with the crystal models (Figure 6b, c). In contrast, the crystalline compound of the model cage 2 is almost nonporous as revealed by a very small BET surface area (4 m2 g-1). The cage-COFs adsorbed 43.8, 22.3 cm3 g-1 (for cage-COF-1), and 37.3, 20.6 cm3 g-1 (for cage-COF-2) of CO2 at 273, 298 K and 1.0 bar, with adsorption enthalpies (Qst) of 28.4 and 32.4 kJ mol-1 at low coverage, respectively (Figures S27-S32). Both the CO2 adsorption amounts and enthalpies are significantly higher than those measured for the cage 2 (24.6, 14.9 cm3 g-1 at 273, 298 K, respectively, and Qst = 16.0 kJ mol-1). Simulations by Metropolis Monte Carlo method using universal force field showed that CO2 adsorption sites are mainly distributed within the cage cavities (Figures S36-S37). As further suggested by DFT calculation, the cooperative interactions of hydrogen-bonding with the two phloroglucinol aromatic protons and lone pair- interactions enabled by the electron-deficient triazines in the Vclefts facilitate the CO2 binding (Figure S38).



Figure 6. (a) N2 adsorption-desorption isotherms at 77 K and the pore size distribution of (b) cage-COF-1 and (c) cage-COF-2. In conclusion, we have synthesized for the first time two cage based crystalline covalent organic frameworks from an easilymade molecular cage. The cage-COFs have a hexagonal skeleton consisting of pillared cage knots and hanging linkers which forms a rippled layer. The unique cage-directed skeleton structure leads to unusual ABC interlayer packing through maximized -stacking of the cage twosided faces. This packing forms trigonal channels surrounded by all -surfaces and interconnected in ab plane which are otherwise inaccessible from traditional 2D COFs. By incorporating in the frameworks, the functional intrinsic cage cavities enable cooperative interactions for enhanced CO2 binding. The successful demonstration of the cage-COFs not only enables the facile hierarchical construction of COFs from simple aromatic fragments with rendered intrinsic cage cavities, but also merges the borderline of 2D and 3D COFs, and bridges the porous organic cages and extended crystalline organic frameworks, which we believe will pave a way for structure-orientated functional molecular material design.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Synthesis, characterization, gas adsorption experiments and modeling details. CCDC 1848320 and 1848321 contain the supplementary crystallographic data for this paper (PDF) Crystallographic data of the cage 1 and cage 2 (CIF)

AUTHOR INFORMATION Corresponding Author [email protected]

Author Contributions ⊥J.-X.

Ma and J. Li contributed equally to this work.

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT Financial supports from National Natural Science Foundation of China (21502200, 21772203, 21521002, 21471009, 21527803) and Chinese Academy of Sciences (QYZDJ-SSW-SLH023) are gratefully acknowledged. Q.-Q. Wang also thanks the Thousand Young Talents Program for the support.

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