Three-Dimensional Open-Framework Germanate Built from a Novel

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A Three-Dimensional Open-Framework Germanate Built From a Novel Ge13 Cluster and Containing Two Types of Chiral Layers Shiliang Huang, Huijuan Yue, Yanping Chen, Yu Liu, Yuxiang Guan, Xiaodong Zou, and Junliang Sun Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01421 • Publication Date (Web): 05 Jan 2018 Downloaded from http://pubs.acs.org on January 7, 2018

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Crystal Growth & Design

A Three-Dimensional Open-Framework Germanate Built From a Novel Ge13 Cluster and Containing Two Types of Chiral Layers Shiliang Huang,‡[a], [b] Huijuan Yue, ‡ [c] Yanping Chen,[d] Yu Liu,[a] Yuxiang Guan,[a] Xiaodong Zou,*[b] and Junliang Sun*[b], [d] [a]

Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900, PR China Berzelii Center EXSELENT on Porous Materials, Department of Materials and Environmental Chemistry, Stockholm University, SE-10691, Stockholm [c] State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, PR China [d] College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, PR China ‡ These authors contributed equally to this work. KEYWORDS: Open-framework germinate, Ge13 cluster, Chiral layer, 3D framework [b]

ABSTRACT: A new open-framework germanate [Ge15O30(OH)4]·2(H2tren), denoted SU-69, was synthesized under hydrothermal conditions with tris-(2-aminoethyl)-amine (tren) as a structure directing agent (SDA). SU-69 crystallizes in a monoclinic space group (C2/c, No.15) with a = 20.2656(7) Å, b = 11.6250(4) Å, c = 18.5602(10) Å and β = 90.528(4) ˚. The framework of SU-69 is built from a novel Ge13O27(OH)2 (Ge13) cluster with two additional GeO3(OH) tetrahedra. Two types of chiral 3,6-net building layers are found in the framework, which are alternately stacked and connected to form a three-dimensional (3D) achiral framework with a two-dimensional (2D) 10×12-ring channel system. The SDA molecules interact with the framework via H-bonds. The thermal stability of as-synthesized SU-69 has also been investigated.

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INTRODUCTION

Crystalline inorganic open frameworks constructed from TOx (T = framework element; x = 4, 5, 6, ···) polyhedral building units are of great interest due to their wide applications in gas adsorption, ion-exchange and catalysis.1-3 As a relatively new member of open-framework materials, germanates have attracted great attention in the past two decades.4-11 In contrast to the TO4 (T = Si, Al) tetrahedra building unit in zeolite frameworks, germanium can have various oxygen coordination forming GeO4 tetrahedron, GeO5 trigonal bipyramid and GeO6 octahedron. Normally, these polyhedral units were further linked into even larger clusters, such as Ge7(O,OH,F)19 (Ge7) cluster,12-16 Ge8(O,OH,F)20 (Ge8) cluster,17-20 Ge9(O,OH,F)25-26 (Ge9) cluster21-26 and Ge10(O,OH)27-28 (Ge10) cluster.27-30 Different connections of these clusters lead to numerous types of frameworks, which is the origin of the structural diversity of germanate frameworks. For example, Ge7 clusters have been found in 0D, 1D, 2D and 3D frameworks.3 More importantly, these large clusters have an advantage in building openframework structures with extra-large pores and very low framework densities, as predicted by Férey in terms of scale chemistry.31-33 For example, the mesoporous germanate SU-M, which is built from Ge10 clusters, has 30-ring channels and possesses the largest primitive cell and lowest framework density of any inorganic material when it was reported.6 Moreover, a combination of different types of clusters can generate exotic frameworks with extra-large pores. The incorporation of Ge7 and Ge9 clusters into the same frameworks has resulted in four germanate compounds,

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SU-8,7 SU-44,7 SU-6410 and JLG-12,9 which have extra-large 16-, 18-, 18- and 30-ring channels, respectively. Recently, a novel mesoporous germanate PKU-17 with a record 48-ring pore has been synthesized by combining Ge7 and Ge10 clusters in the same framework.34 As the cluster building units play an important role in the construction of germanate frameworks, searching for new types of cluster building units and studying the framework architecture from the cluster building units are critical for the discovery of novel germanate frameworks.35 Open-framework compounds with chiral frameworks and channels are particularly desirable for their potential applications in enantioselective sorption, separation and catalysis.36-37 However, there are only a few inorganic open-framework materials with chirality.6,8,38-54 Among them, packing of 2D building layers in a helical fashion along a screw axis is found to be efficient to form helical channels as well as a chiral framework. For example, chiral zeolite framework *BEA is built from building layers with the adjacent layers correlated by a rotation of 90˚,38-40 while in SU-32 the rotation angle is 60˚ to form a 61 screw axis.8 When the building layer is chiral, chiral framework can be formed in a more flexible manner. For example, chiral metal phosphates can be obtained by either stacking 4,6-net sheets in a ABCDE sequence following a 65 screw axis or in a ABAB sequence correlated by a 2-fold axis.55-58 Therefore, new types of chiral 2D building layers have potential in the construction of new chiral frameworks. Here, we report a three-dimensional open-framework germanate, SU-69, which contains chiral 3,6-net building layers constructed with a novel Ge13O27(OH)2 (Ge13) cluster and two additional GeO4

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tetrahedra. The Ge13 cluster consists of a relatively rigid Ge3 core and ten surrounding GeO4 tetrahedra, and can be considered as a derivative of Ge9 clusters. The structure directing agent (SDA) molecule was diprotonated and interacts with the framework via 5 H-bonding.

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EXPERIMENTAL SECTION

Synthesis. SU-69 was synthesized under hydrothermal conditions using tris-(2-aminoethyl)-amine (tren) as SDA. In a typical synthesis, 100 mg germanium dioxide, 2.0 mL tren and 2.0 mL water, with a molar ratio of GeO2/tren/H2O=1/13.4/116.2, were mixed to form a clear solution. The solution was transferred into a 30 mL Teflon-lined stainless-steel autoclave and heated at 160 °C for 5 days. After filtration, washing with deionized water and drying at room temperature, colourless plate crystals were obtained, as shown in Figure S1 in the Supporting Information. A crystal with a size of about 1×5×10 µm3 was selected for crystallographic study. Structure Determination. Single-crystal X-ray diffraction data were collected using synchrotron radiation (λ = 0.9077 Å) at the Beamline I711, MAX-IV Laboratory, Lund, Sweden. Data reduction and empirical absorption correction were applied with CrysAlisPro, and the structure was solved and refined by SHELX.59 All non-hydrogen atoms were located from the single crystal X-ray diffraction data. Crystallographic details of the structure refinement are given in Table 1. The atomic coordinates and equivalent isotropic displacement parameters can be found in the cif file in the Supporting Information. The cif file (CCDC1509595) can be also obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif. The powder X-ray diffraction pattern simulated from the refined structure model is consistent with the experimental pattern, as shown in Figure S2 in the Supporting Information.

ture refinement, [Ge15O30(OH)4]·2(H2tren). CNH analysis showed the composition of C, N and H were 7.64, 5.74 and 2.29 wt%. The molar ratio of C/N=1.55 indicates the SDA molecules are intact (calculated N/C=1.5). The hydrogen content is consistent with the 45 sum of hydrogen in the framework terminal -OH group and tren molecules (2.28 wt%). Thermogravimetric analysis (TGA) and in situ powder X-ray diffraction (PXRD) was used to study the thermal stability of the compound.

SU-69

chemical formula formula mass crystal system a/Å b/Å c/Å α/° β/° γ/° unit cell volume/Å3 temperature/K space group No. of formula units per unit cell, Z radiation type, wavelength /Å absorption coefficient, µ/mm-1 No. of reflections measured No. of independent reflections Rint Final R1 values (I > 2σ(I)) Final wR(F2) values (I > 2σ(I)) Goodness of fit on F2

[Ge15O30(OH)4]·2(H2tren) 1933.82 monoclinic 20.2656(7) 11.6250(4) 18.5602(10) 90.00 90.528(4) 90.00 4372.4(3) 298(2) C2/c (No. 15) 4 Synchrotron, 0.9077 19.305 3475 2123 0.1019 0.0895 0.2575 0.1390

Other Characterizations. Solid-state 1H MAS NMR measurement was performed for the confirmation of the protonation of 35 SDA molecules. Two signals were observed. The single at 7.4 ppm can be attributed to the resonance of -NH3 groups of tren, while that at 2.5 ppm corresponds to the -NH2 and -CH2- groups of tren, as shown in Figure S3 in the Supporting Information. The carbon, hydrogen, and nitrogen (CHN) elemental analysis were 40 applied to confirm the chemical formula deduced from the struc2

RESULTS AND DISCUSSION

50 Structure Building Unit. SU-69 crystallizes in a monoclinic

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Table 1. Crystallographic data and structure refinement details for SU-69 compound reference

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space group (C2/c, No.15) with a = 20.2656(7) Å, b = 11.6250(4) Å, c = 18.5602(10) Å and β = 90.528(4) ˚. The framework is built from a novel Ge13O27(OH)2 (Ge13) cluster building unit and two additional GeO3(OH) tetrahedra. The Ge13 cluster consists of one GeO6 octahedron, two GeO5 trigonal-bipyramids and ten GeO4 tetrahedra, as shown in Figure 1. The octahedron and two trigonalbipyramids are connected to form a 3-ring core (Ge3), which is encapsulated by ten tetrahedra. All polyhedral building units are connected via corner-sharing oxygen atoms. According to their positions relative to the core, these ten GeO4 tetrahedra can be divided into two sets. Six of them are nearly on the same plane with the core, named equator tetrahedra, while two above or two below the core, denoted north-pole and south-pole tetrahedra, respectively, as shown in Figure 1b. It is found that the north-pole and south-pole tetrahedra can coordinate to the 3-ring core in different manners, resulting six disordered forms of the Ge13 clusters, see Figure S4 in the Supporting Information. With such a packing of polyhedral building units, the entire Ge13 cluster shows a highest symmetry of C2. The Ge-O bond lengths in the GeO4 tetrahedra (from 1.68(2) to 1.80(4) Å) and in the GeO5 trigonal bipyramids and GeO6 octahedra (1.698(14)-2.108(7) Å) agree with those in the literature.5 The list of the Ge-O bond lengths and Ge-O-Ge angles are given in Table S1 and S2 in the Supporting Information, respectively.

Figure 1. The Ge13 cluster building units of SU-69 framework represented in (a) ball-stick mode and (b) polyhedral mode. The Ge13 cluster consists of a center 3-ring core and ten surrounding GeO4 tetrahedra. Color codes for the polyhedra: Red, GeO6 octahedron; Yellow, GeO5 trigonalbipyramid; Green, equator GeO4 tetrahedron; Blue, north- and south-pole tetrahedra.

Framework. In SU-69, the Ge13 clusters adopt a C-centering lattice arrangement and are connected by additional GeO3(OH) tetrahedra to form a building layer in the ab plane at z = 0.25, as shown in Figure 2a. Within the layer, each additional GeO3(OH) tetrahedron connects to three Ge13 clusters and each Ge13 cluster 80 connects to six neighbouring ones via six additional GeO3(OH) tetrahedra. Therefore, the building layer can be transformed into a two-dimensional 3,6-net, if the Ge13 cluster and additional GeO3(OH) tetrahedron are simplified as two different nodes. Due to the c-glide symmetry operation involved in the C2/c space 85 group, another layer with similar 3,6-net was generated at z = 0.75, as shown in Figure 2c. The two 3,6-net layers contain helical 6-ring chains with different handedness, which is formed by the 75


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Figure 2. The structure of the SU-69 framework. (a) The R-layer and (c) L-layer in the ab plane at the height of z = 0.25 and z = 0.75, respectively; (b) the right-handed and (d) left-handed helical chains within the R-layer and L-layer, respectively; (e) the alternative stacking of the R- and L-layers along the caxis; the interlayer connection viewed along (f) the b-axis and (g) [1-10] direction; (h) a binodal 3,8-connected net derived from the SU-69 framework as the Ge13 clusters and the additional GeO3(OH) tetrahedra are simplified as green and purple nodes, respectively. The additional GeO3(OH) tetrahedra are coloured in purple.

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equator GeO4 tetrahedra of Ge13 clusters and the additional GeO3(OH) tetrahedra via corner-sharing. At z = 0.25, the chains run around the 21 screw axis in a right-handed manner, and are symmetry-related by a 2-fold rotation, as shown in Figure 2b. In contrast, left-handed helical chains are found in the layer at z = 0.75, as shown in Figure 2d. In this case, the 3,6-net layers at z = 0.25 and z = 0.75 reveal opposite chirality and are, therefore, named as R-layer and L-layer, respectively. These 3,6-net layers stack alternately along the c-axis with the Ge13 clusters on top of each other, forming the 3D framework of SU-69, as shown in Figure 2e. The layers are connected via the north-pole and south-pole tetrahedral pairs of the Ge13 clusters leading to the formation of 4-rings, as shown in Figure 2f and 2g. Corresponding to the six configurations of the Ge13 cluster due to the disorder, each 4-ring has three possible orientations, see Figure S5 in the Supporting Information. Based on these inter-layer connections, the SU-69 framework has a topology of a binodal 3,8-connected net (Figure 2h) and a chemical composition of [Ge15O30(OH)4]4- with a low framework density of 13.7 Ge/1000Å3. Channel System. In SU-69, 12-ring channels are found along the b-axis between the 3,6-net layers. These channels communicate with each other via 10-ring windows, forming 10-ring channels in the [110] direction. The pore dimensions of the 10- and 12rings are 6.67 Å × 10.45 Å and 6.74 Å × 9.38 Å, directly measured from the distance between the centres of the bridging Oatoms. Although there exists 7-rings within the R- and L-layers, they are very elliptical and considered as solvent inaccessible. Therefore, the SU-69 framework has a 2D 10×12-ring channel system, as shown in Figure 3. SDA Molecules. The tren molecules located within the 10×12-ring channels. Both interact with the framework via Hbonds with a Ge4 structure motif which is formed by the addition-

Figure 3. The 2D 10×12-ring channel system in SU-69 together with the 10-ring and 12-ring represented in a polyhedral mode. The dimension of the 10-ring and 12-ring are 6.67×10.45 Å and 6.74×9.38 Å, directly measured from the distance between the centres of the bridging O-atoms.

al GeO3(OH) tetrahedron and three connected equator tetrahedra, 35 as shown in Figure 4a and 4b. The distance between the N-atoms

of the SDA molecules and the O-atoms on the Ge4 motif ranges from 2.712 Å to 3.074 Å and the details of the H-bonds can be seen in Table S3 in the Supporting Information. These Ge4 moieties show a geometric match with the SDA molecules. Moreover, 40 the six configurations of the Ge13 cluster as well as the three orientations of the interlayer 4-rings can be considered symmetryrelated by a pseudo 3-fold rotation, which is also consistent with the geometry of the SDA molecules. All these might indicate structure directing effects from the SDA molecules to the frame45 work.

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Figure 4. The H-bonding interactions of the SDA molecules in the (a) Rlayer and (b) L-layer. The geometric matching between the SDA molecule and the Ge4 moiety in each layer is marked with a black circle, which is further magnified. The SDA is shown as blue sticks and the H-bonds (N(H)…O) as red dashed lines.

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Chirality. Although the SU-69 framework is achiral due to the ···RLRLRL··· stacking sequence of the 3,6-net layers, a chiral framework can be constructed by replacing of the L-layers by Rlayers or vice versa. The cif files for the hypothetic chiral frameworks built from the R-layers and L-layers, named SU-69A and SU-69B, can be seen in Supporting Information and obtained via www.ccdc.cam.ac.uk/data_request/cif with CCDC-1509596, 1509597). In this case, the space group symmetry was reduced from C2/c of SU-69 to C2 of the hypothetic framework, see Table S4 in the Supporting Information. In order to generate similar inter-layer connection of the 4-rings, different disordered configurations were adopted for the Ge13 clusters in adjacent layers (Figure S6 in the Supporting Information). With the ···RRR··· or ···LLL··· stacking sequence of the 3,6-net layers, the hypothetic framework can have different chirality but the same topology as that for SU-69. All the Ge-O bond lengths and Ge-O-Ge angles in the hypothetical frameworks are reasonable (Table S5 and S6 in the Supporting Information). Thermal Stability. TG-DSC measurement and in situ PXRD were performed on the as-synthesized SU-69 to investigate its thermal stability, as shown in Figure 5 and 6. The weight loss of 1.9% from 35°C to 100°C comes from the removal of adsorbed water, while that between 100°C and 400°C can be attributed to the partial release of the SDA molecules. The decomposition of the SDA molecules was observed at about 350°C, as indicated by the sharp weight loss in the TG curve and the endothermic peak in the DSC curve. The continuing of the SDA decomposition and consequently the collapse and condensation of the framework lead to the weight loss from 400°C to 700°C. The total weight loss between 100°C and 700°C is 17.6%, which is consistent with the calculated value from the structure model (18.5%) considering the water adsorption. The collapse of the framework can be also evidenced by the disappearance of most diffraction peaks in PXRD patterns above 350°C, as shown in Figure 6. To remove SDA, the as-synthesized sample was also treated by O3 at low temperature for 10 hours. However, it became amorphous after the oxidation of the SDA molecules. Based on these results, it was concluded that the framework collapse of SU-69 after removing SDAs originates from the strong H-bonding interactions between the framework and SDA molecules, and also the space filling effect of SDA molecules. The reservation of framework after removing SDA molecules is still a big challenge not only for SU-69 but also for many other open-framework germanates.

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Figure 5. TG-DSC measurement of as-synthesized SU-69 in air with a heating rate of 5 °C·min-1.

Figure 6. In situ X-ray powder diffraction of as-synthesized SU-69. The sample was heated in vacuum to 450°C with 10°C/min and X-ray powder diffraction data were collected at each step.

CONCLUSIONS

We have synthesized a new open-framework germanate, SU-69, constructed from a novel Ge13O27(OH)2 (Ge13) cluster and two additional GeO3(OH) tetrahedra. SU-69 contains two types of chiral 3,6-net layers with opposite chirality. These two 3,6-net layers stack alternately along the c-axis and are connected to each 50 other via inter-layer 4-rings to form a 3D framework. Although the framework of SU-69 is achiral, a hypothetic chiral framework can be derived from it. The tren molecules show a structure directing effect on the framework via hydrogen bonding interactions. Unfortunately, the framework collapsed when the SDA molecules 55 were removed from the structure at about 300°C. The discovery of the novel Ge13 cluster as well as the chiral 3,6-net layers provides new structure building units for constructing new types of chiral frameworks. In the case of SU-69 as well as other openframework germanates, the reservation of framework after remov60 ing SDA molecules is still a big challenge. 45

ASSOCIATED CONTENT

Supporting Information 4


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The experimental and simulated PXRD patterns of SU-69; SEM images; 1H MAS NMR; TG-DSC curves; crystallographic information files of SU-69 and the hypothetic frameworks. This material is available free of charge via the Internet at 5 http://pubs.acs.org. Accession Codes CCDC 1509595-1509597 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 10 data_ [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION Corresponding Author 15 * E-mail: [email protected] (J. S.).

* E-mail: [email protected] (X. Z.).

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Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT

20 This project is supported by the Presidential Foundation of CAEP

(Grant No. 201501018), National Natural Science Foundation of China (No. 21527803, 21471009), the Swedish Research Council (VR) and the Swedish Governmental Agency for Innovation Systems (VINNOVA) through the Berzelii Center EXSELENT 25 and the MATsynCELL project through the Röntgen-Ångström Cluster. We also thank the staffs at Max IV Laboratory in Lund, Sweden for the assistant of data collection and Dr. Ningning Wu at the Center for Physicochemical Analysis and Measurements in Institute of Chemistry Chinese Academy of Science for measuring 30 the NMR measurement.

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A Three-Dimensional Open-Framework Germanate Built From a Novel Ge13 Cluster and Containing Two Types of Chiral Layers Shiliang Huang,‡[a], [b] Huijuan Yue, ‡ [c] Yanping Chen,[d] Yu Liu,[a] Yuxiang Guan,[a] Xiaodong Zou,*[b] *[b], [d] 5 and Junliang Sun Synopsis A 3D open-framework germanate, [Ge15O30(OH)4]·2(H2tren), denoted SU-69, is built from a novel Ge13O27(OH)2 (Ge13) cluster and containing two alternately stacking chiral 3,6-net building layers.

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Three-Dimensional Open-Framework Germanate Built from a Novel

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