An Open-Framework Aluminophosphite with Face-Sharing AlO6

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An Open-Framework Aluminophosphite with Face-Sharing AlO6 Octahedra Dimers and Extra-Large 14-Ring Channels Cong Lin, Fengjuan Pan, Jian Li, Yanping Chen, Dier Shi, Tianqiong Ma, Yanquan Yang, Xin Du, Wei Wang, Fuhui Liao, Jianhua Lin, Tao Yang, and Junliang Sun Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01636 • Publication Date (Web): 03 Feb 2018 Downloaded from http://pubs.acs.org on February 5, 2018

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Crystal Growth & Design

An OpenOpen-Framework Aluminophosphite with FaceFace-Sharing AlO6 Octahedra Dimers and ExtraExtra-Large 1414-Ring Channels Cong Lin,†,‡ Fengjuan Pan,‡ Jian Li,‡ Yanping Chen,‡ Dier Shi,‡ Tianqiong Ma,§ Yanquan Yang,‡ Xin Du,‡ Wei Wang,§ Fuhui Liao,‡ Jianhua Lin,‡ Tao Yang,*,† and Junliang Sun*,‡ †

College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331, China

‡

College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.

§

College of Chemistry and Chemical Engineering, Lanzhou University, Gansu 730000, China.

Supporting Information ABSTRACT: PKU-25Al, an open-framework aluminophosphite possessing extra-large intersecting 14-ring (14R) channels and a novel Al/P ratio of 9/14, was hydrothermally synthesized using commercially available 4-dimethyaminopyridine (DMAP) as organic structure-directing agents (OSDA). Two types of secondary building units (SBUs), SBU-1 with 6*1 units and racemic SBU-2 composed of two chiral 4=1 units, are utilized to construct the porous layers with a 4.6.12-net topology and the chains with unprecedented face-sharing AlO6 octahedra dimers, respectively. Stringing the ABAB stacked layers via the chains would achieve the PKU-25Al framework with a unique topology as well as numerous chiral channel motifs. Meanwhile, the protonated DMAP molecules interact with the inorganic framework through hydrogen bonding and reside in the voids with an exceptional triangular pattern. PKU-25Al is the first aluminophosphite with extra-large channels and enriches the materials chemistry of the open-framework families with exceptive structures. extra-large channels,21-22 such as JIS-3 (18R),23 Cr-NKU-24 (24R),24 ZnHPO-CJ1 (24R),25 NTHU-5 (26R),26 as well as the NTHU-13 family with tunable pores varying from 24R to 72R.27 However, nearly all of these extra-large-channel phosphites require the participation of transition metal elements, while the main-group metal phosphites exhibit much less kinds and smaller channels, with the largest 24R channels in beryllium phosphite SCU-2428 and 18R channels in gallium phosphite NTHU-15.29 What is more, there are very few studies devoted to the open-framework aluminophosphites, and no extra-large channels has been accomplished in such a field. Actually, to the best of knowledge, only three examples of open-framework aluminophosphites have been synthesized so far, i.e., NKX-2,30 NKX-6,31 and [(CH3)2NH2]1.5·(H3O)0.5·[Al4(HPO3)7(H2O)3]·(H2O)0.5,32 all of which possess 12R channel systems. Consequently, it still remains greatly challenging to acquire the open-framework aluminophosphites, especially those with extra-large channels. In this study, we report the first aluminophosphite, [(C7H11N2)(H3O)0.21][Al3(HPO3)4.67O0.13(OH)0.62(H2O)2]·(H2O)2.0 9 (denoted PKU-25Al), with extra-large 14R channels and an exceptional framework topology. It was prepared as a pure phase (Figure 1) by the hydrothermal reaction of a mixture containing Al(OiPr)3, H3PO3, DMAP and H2O with a 1:2.4:3:(10-20) ratio at 433 K for 5 days in a Teflon-lined stainless-steel autoclave (see the Synthesis part in the Supporting Information). Single-crystal structural analysis revealed that PKU-25Al crystallized in the P-31c space group (see the Structure Determination part in the Supporting Information and Table S1), leading to the crystals with hexagonal plate-like morphology (Figure S2). Each asymmetric unit of PKU-25Al contains 24 unique non-hydrogen atoms, including 3 Al, 3 P, and 9 O atoms, and one protonated DMAP molecule (Figure S1). The bond lengths of Al-O and P-O (Table S3) are in good accordance with those observed in other

Crystalline inorganic materials with open-framework structures, such as zeolites and aluminophosphate molecular sieves, constitute one of the most extensively studied research areas of material science due to their rich structural chemistry and widely spread industrial applications in catalysis, ion exchange, gas adsorption, and separation.1-5 Since the structure determination of the cacoxenite mineral with 36R channels6 and the discovery of the aluminophosphate molecular sieve VPI-5 with 18R channels,7 exploitation of novel open-framework materials with extra-large channels has been of particular industrial interest so that one can perform shape-selective catalysis and separation on large molecules. So far, two synthetic strategies have been validated effectively in achieving the inorganic frameworks with extra-large channels. One approach is to use large polyhedral clusters as secondary building units (SBU), known as the scale chemistry proposed by Férey,8-9 which has already led to the construction of a large variety of materials with extra-large channels, such as cloverite (20R),10 NTHU-1 (24R),11 JLG-12 (30R),12 SU-M (30R),13 SUT-7 (38R),14 and PKU-17 (48R).15 Another feasible route for generating more open structures is to introduce three-connected other than four- or five-connected polyhedra as primary building units (PBU), e.g. the terminal-containing [O-SiO3], [HO-PO3]2-, [O=PO3]3-, and [BO3]3-, resulting in numerous materials with extra-large channels, for instance, JDF-20 (20R),16 DNL-1 (20R),17 PKU-2 (24R),18 ITQ-43 (28R),19 and ITQ-37 (30R).20 Meanwhile, a more controllable and important method to deliberately utilize the three-connected groups is the judicious choice of those reactants with intrinsic three-connected nature, among which the phosphorous acid with P-H terminals is the most representative. Notably, the employment of the pseudo-pyramidal [HPO3]2groups instead of the tetrahedral [PO4]3- groups would greatly reduce the M-O-P (M = metal ions) linkages and therefore, tend to generate novel interrupted open-framework structures with 1

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aluminophosphites.30-32 The AlO6 octahedra share the bridging O atoms with the pseudo-pyramidal [HPO3]2- groups and AlO6 octahedra to construct the inorganic framework of PKU-25Al.

indicated by the relatively longer Al-O bond (1.997(2) Å) and single-crystal structural analysis. Similar assignments have previously been described in metal phosphates and phosphites.33-34 The bonded water molecules further interact with neighboring O atoms through hydrogen bonding (O(8W)-H(8A)···O(2), O(8W)-H(8A)···O(5), and O(8W)-H(8B)···O(6)) to stabilize the structure. Three Al(1) and three P(2) atoms are first alternatively connected via the bridge O atoms to form a 6R, which is afterwards capped by a [HP(1)O3]2group, resulting in the 6*1 unit (designated as SBU-1, Figure 2j). Such a building unit is common and has been exhibited in other open-framework structures.34-40 In PKU-25Al, each SBU-1 connects three neighboring units through edge-sharing, forming a two-dimensional (2D) porous layer with 4-, 6- and 12-rings (Figure 2c), also known as the 4.6.12-net in the ab plane. Layered structures with the same topology have previously been reported in some aluminophosphates, but the Al atoms in those structures are in tetrahedral environments and share all the corners with the three-connected PO4 tetrahedra possessing P=O or P-OH terminals,39,41-42 which obviously differ from those in PKU-25Al. With regard to the Al(2) and Al(3A) atoms, they are firstly connected via three [HP(3)O3]2- groups and thereafter integrated as two kinds of [3.3.3] propellane-like chiral 4=1 units, as shown in Figure 2g and 2k. Notably, the difference between those chiral units

Figure 1. Powder X-ray diffraction (PXRD) patterns of the as-made and simulated PKU-25Al from single crystal structure. For the Al(1)O6 octahedron, all but one of the O atoms bridge five P atoms to achieve the five connection. The exception is the O(8W) atom, which is assigned as a terminal water molecule, as

Figure 2. Construction of the PKU-25Al framework. Aluminophosphite framework with the extra-large 14R channels along the a-axis (a) and c-axis (b). (c) 2D porous layer with the 4.6.12-net topology in the ab plane. (d) 1D chain. The 2D layers and 1D chains in (a), (b), (c) and (d) are shown in ball-and-stick and partially transparent polyhedral model, respectively, while the DMAP molecules are omitted for clarity. (e) Racemic SBU-2 composed of two chiral 4=1 units via sharing the Al(2) atom. (f) SBU-2 viewed along the c-axis. (g) Chiral 4=1 unit with configuration and (h) viewed along the c-axis. (i) Face-sharing AlO6 octahedra dimer. (j) SBU-1: the 6*1 unit. (k) Chiral 4=1 2


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unit with Δ configuration and (l) viewed along the c-axis. (e), (g), (i), (j) and (k) are shown in ball-and-stick model, while (f), (h) and (l) are shown in stick model. severe quadrupole broadenings (see the Structure Determination part and Characterization part in the Supporting Information and Figure S3).51-54 The distortion of the AlO6 octahedra in PKU-25Al was calculated using the formula proposed by Shannon to describe the chirality degree.55-56 The calculated distortion for Al(2)O6 is zero owning to the unique location, while the calculated values for Al(1)O6 and Al(3A)O6 are 74.73 and 59.14 (× 10-5), respectively. Such values are very large in the Al-based structures and reveal some severe distortion of those octahedra,55 which is believed to be responsible for the formation of the chiral 4=1 units and the chiral channel motifs, as discussed below. In PKU-25Al, a series of 2D layers stacks in the ABAB sequence along the c-axis, further perpendicularly penetrated through the 12R by the 1D chains. As a result, the lamellae are anchored through the bonding of the Al(1) atoms with the [HP(3)O3]2- groups to accomplish the Al(1)O6 octahedra; therefore, the three-dimensional (3D) inorganic open-framework structure is achieved, as shown in Figure 2a and 2b. The novel atom ratio of Al/P in PKU-25Al is 9/14, which was verified by various techniques (see the Characterization part in the Supporting Information and Figure S5). Such a ratio has not previously been observed in any structures.39 Meanwhile, a 2D extra-large 14R-channel system along the a- and b-axis and [110] direction is also accomplished in PKU-25Al (Figure 2a and S9). Up to date, only three open-framework aluminophosphites with 12R channels have been reported,30-32 and therefore, PKU-25Al is the fourth and also the first extra-large-channel aluminophosphite possessing the largest 14R channels. The calabash-like 14R channel window (~8.5 × 3.1 Å) is shown in Figure 3a, and it is worthwhile mentioning that via sharing two [HP(1)O3]2- groups, three 14R windows are hence combined and constitute two kinds of unprecedented chiral clover-like channel motifs, similar to the smaller chiral 4=1 units in the 1D chains. As shown in Figure 3b and 3c, the chiral channel motifs twisting in the left- and right-hand directions along the c-axis are designated as and Δ configurations, respectively. Such chiral channel motifs are very rare and only one indium phosphate with similar chiral motifs has been reported.33 Therefore, numerous chiral 4=1 units and channel motifs exist in the PKU-25Al framework, which are alternately arranged, resulting in an achiral structure (Figure S10).

is their configuration, with the and Δ configuration twisting in the left- and right-hand directions along the c-axis, respectively (Figure 2h and 2l). Similar chiral units have previously been demonstrated in several indium phospates33,43-44 and metal phosphites.32,34,45 Although similar 4=1 units have also been observed in NKX-230 and one zinc phosphite,40 those 4=1 units in their structures are achiral due to the mirror symmetry. In PKU-25Al, the two chiral units are subsequently combined via sharing the Al(2) atoms, constituting the racemic SBU-2 (Figure 2e and 2f). Therefore, the Al(2) atoms are connected by six adjacent [HP(3)O3]2- groups to achieve the Al(2)O6 octahedra. Whereafter, adjacent SBU-2 are linked via bonding the two Al(3A) atoms by three hydroxyl (–O(9A)H) groups, consequently leading to the face-sharing Al(3A)O6 octahedra dimers (Figure 2i) and the one-dimensional (1D) chains along the c-axis (Figure 2d). The existence of the -O(9A)H groups rather than O atoms in the face-sharing octahedra dimers was identified from the single-crystal structural refinements and further verified by the bond valence sums (BVS) calculations. Accordingly, the Al(3A) atoms are four-connected with three [HP(3)O3]2- groups and one Al(3A) atoms via three -O(9A)H groups, inducing the Al(3A)O6 octahedra. Similar linkages of the hydroxyl groups bonding two Al atoms have also been found in some aluminophosphates,46-49 which however do not lead to the face-sharing AlO6 dimers. In Al(3A)O6 octahedra, the bond length of Al(3A)-O(9A) is a little longer than that of Al(3A)-O(7) and obviously shorter than that of Al(1)-O(8W), implying the exceptive connectivity of the O(9A) atoms, which are three-connected (µ3-O). According to the literature, such a dimer composing of face-sharing AlO6 octahedra is very rare. And to the best of our knowledge, only two open-framework structures possessing similar face-sharing AlO6 octahedra dimers have been investigated. One is the aluminophosphite NKX-230 and the other is the organic-inorganic hybrid silicoaluminophosphate ECR-40A.50 Although the face-sharing O atoms in NKX-12, ECR-40A and PKU-25Al are all µ3-O, the main difference is the origin of the face-sharing O atoms, which are from the large [HPO3]2- groups, larger organic ammonium molecules and much smaller hydroxyl groups in NKX-2, ECR-40A and PKU-25Al, respectively. It is taken into account that those large bonded groups in NKX-2 and ECR-40A are very critical for the stabilization of the face-sharing AlO6 octahedra dimers, which also conversely block the channels to some extent. In PKU-25Al, however, no such large groups rather than the H atom is bonded to the O atoms, which has never been observed in the Al-based open-framework structures. Meanwhile, it is thought that the hydrogen bonding interaction also exists between the face-sharing hydroxyl groups and the disordered water molecules to stabilize the face-sharing dimers since a large amount of water has been indicated from the thermogravimetric-differential scanning calorimetry-mass spectrometry (TG-DSC-MS) coupling technique (see the Characterization part in the Supporting Information and Figure S6). Therefore, the face-sharing AlO6 octahedra dimers in PKU-25Al are unprecedented and of particular interest and structural significance. The Al-O bond lengths and Al-Al distances of the face-sharing octahedra dimers in PKU-25Al, NKX-2 and ECR-40A are shown in Figure S8, which also verifies the rationality of the face-sharing dimers in PKU-25Al. Meanwhile, it remains a necessity to notice that the single-crystal structural analysis also indicated that the Al(3A)O6 octahedra dimers were not fully occupied due to the coexistence of a small amount of Al(3B)O4 tetrahedra, which unfortunately could not be easily detected from the magic angle spinning nuclear magnetic resonance (MAS NMR) due to the too low concentration and the

Figure 3. Channel motifs in PKU-25Al. (a) Extra-large 14R channel window shown in partially transparent polyhedral model. (b) Chiral channel motif with configuration. (c) Chiral channel motif with Δ configuration. (b) and (c) are shown in stick model with the bridge O atoms omitted for clarity. The Al atoms are 4-, 5- and 6-connected while all P atoms are 3-connected, which conduces to four kinds of tiles for constructing the unique tiling structure of PKU-25Al (Figure 4). Another remarkable feature is the low framework density (FD), 3 which is ~13.6 T per 1000 Å (T represents P and Al atoms). Such a value is the lowest among the open-framework 3



aluminophosphites and the structures containing face-sharing AlO6 octahedra dimers.30-32,50 It is also lower than that of the materials containing the 6*1 units34-40 and even the structures with much larger channels, such as the 18R-channel JIS-323 and 20R-channel zinc phosphite.57 The solvent accessible volume (SAV) of PKU-25Al is ~41.7% (~1414 Å3) of a unit cell volume, which is the largest in aluminophosphites and a little smaller than that of NTHU-111 and ND-158 with 24R channels. Therefore, such low FD and high SAV values validate the open-framework nature of PKU-25Al. Owning to the symmetry mismatch with the inorganic framework, the location of the DMAP in PKU-25Al is a little disordered. All the nitrogen atoms on the aromatic ring are protonated and interact with the inorganic framework through hydrogen bonding (N(1)-H(N1)···O(7)), which is also thought to stabilize the structure (Figure S11a). Meanwhile, the supramolecular assembly templating (SAT) phenomenon is also presented in PKU-25Al since three DMAP molecules residing near the three windows of the chiral 14R channel motif constitute the triangle-like trimers in the voids (Figure S11b), leading to the unprecedented triangular arrangement of the DMAP molecules (Figure S11c). It is also believed that such a SAT effect contributes effectively to directing the PKU-25Al structure,37,59 which is also obviously different from that of the parallel cumulated DMAP molecules in aluminophosphates.37,60 Nonetheless, it is a pity that those organic species could not be simply removed due to the strong electrostatic and hydrogen-bonding interactions with the framework. Actually, the PKU-25Al framework would totally collapse before ~573 K prior to the decomposition of the DMAP molecules, as indicated by the TG-DSC-MS measurement (Figure S6) and the in situ variable temperature PXRD (Figure S7). Thus the extra-large 14R channels in PKU-25Al could not be easily accessed, as indicated by the N2 sorption measurements (Figure S14).

Synthesis; structure determination and refinements, and crystallographic information; characterizations including high resolution PXRD, field-emission scanning electron microscope (SEM), 27Al MAS NMR, Fourier transform infrared spectroscopy (FT-IR), energy dispersive spectroscopy (EDS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), element analysis (EA), TG-DSC-MS, in situ variable temperature PXRD, fluorescence and ultraviolet-visible (UV-Vis) spectra and N2 sorption isotherms.

Accession Codes CCDC 1818343 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

■ AUTHOR INFORMATION Corresponding Author * [email protected], [email protected].

Notes The authors declare no competing financial interests.

■ ACKNOWLEDGMENT We thank Prof. Xiaolong Liu (Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences) for discussions in the MAS NMR. This work was supported by the National Basic Research Program (Nos. 2013CB933402, 2016YFA0301004) and National Natural Science Foundation of China (Nos. 21671028, 21527803, 21471009, 21621061).

■ REFERENCES

Figure 4. Tiling structure of PKU-25Al. (a) Four types of tiles. (b) Tiles accumulation pattern. On all accounts, the first extra-large-channel aluminophosphite, PKU-25Al, was synthesized with a novel topology and Al/P ratio. Numerous chiral species and unprecedented face-sharing AlO6 octahedra dimers are found in the PKU-25Al framework. The compound described here not only makes up for the absence of the extra-large channels in aluminophosphites but also possesses particular chemical interest and structural significance. Further extending to the gallium and indium phosphite systems, isostructural materials and other interesting structures have also be prepared and related work will be reported elsewhere.

■ ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.xxxxxxx.

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An OpenOpen-Framework Aluminophosphite with FaceFace-Sharing AlO6 Octahedra Dimers and ExtraExtra-Large 1414-Ring Channels Cong Lin,†,‡ Fengjuan Pan,‡ Jian Li,‡ Yanping Chen,‡ Dier Shi,‡ Tianqiong Ma,§ Yanquan Yang,‡ Xin Du,‡ Wei Wang,§ Fuhui Liao,‡ Jianhua Lin,‡ Tao Yang,*,† and Junliang Sun*,‡ †

College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331, China

‡

College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.

§

College of Chemistry and Chemical Engineering, Lanzhou University, Gansu 730000, China.

Table of Content Graphic

Synopsis The first open-framework aluminophosphite with extra-large intersecting 14-ring channels and a unique Al/P ratio of 9/14, was herein reported. This material possesses an exceptional framework topology with numerous chiral species and unprecedented face-sharing AlO6 octahedra dimers, which makes up for the absence of extra-large channels in the aluminophosphites and enriches the materials chemistry of the open-framework families with exceptive structures.


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An Open-Framework Aluminophosphite with Face-Sharing AlO6

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