Supertetrahedral Cluster-Based InâSe Open Frameworks with Unique

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Supertetrahedral Cluster-Based In-Se Open Frameworks with Unique Polyselenide Ion as Linker Chaozhuang Xue, Jian Lin, Huajun Yang, Wei Wang, Xiang Wang, Dandan Hu, and Tao Wu Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 09 Apr 2018 Downloaded from http://pubs.acs.org on April 9, 2018

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Crystal Growth & Design

Supertetrahedral Cluster-Based In-Se Open Frameworks with Unique Polyselenide Ion as Linker Chaozhuang Xue, Jian Lin, Huajun Yang, Wei Wang, Xiang Wang, Dandan Hu, Tao Wu* College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China.

ABSTRACT: Reported here are three new In-Se open frameworks with unique polyselenide ion as linker. Single-crystal X-ray diffraction analyses demonstrate that supertetrahedral Tn (n = 2, 3) clusters serving as secondary building units in these compounds are connected via polyselenide ligands to form the interrupted or elongated diamond topologies. UV-Vis absorption analysis and photoelectric response measurements indicate that these In-Se frameworks retain semiconductor properties, making them potential candidates in photocatalytic applications.

Open-framework chalcogenides have attracted extensive attention over the past few decades because these materials integrating porosity with semiconducting properties may find various newlyemerging applications, such as fast ion conductors, sequestration of heavy metals and visible-lightdriven photocatalysts.1-5 In the meanwhile, a considerable amount of multifarious chalcogenide frameworks have been obtained via diverse assemblage of various of tetrahedrally shaped secondary building units (SBUs, such as Tn, Pn and Cn clusters), the size of which can be controlled through introducing metal cations with different valence state.6 It is worth noting that among numerous metal chalcogenide frameworks, the proportion of selenides is less than sulfides, which severely impacted the exploration of selenide frameworks on their potential applications, especially in electrocatalysis,

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photocatalysis and photoelectrochemistry.7-10 There are more difficulties for the selenides in forming big Tn-type SBUs than the sulfides. The internal reason may be that the bond lengths of M-Se, compared to those of M-S, have big changing for the different type of metal ions, which do not facilitate the formation of big-sized selenide Tn cluster due to big mismatch between M-Se bonds. For example, large amount of sulfide-based T5 clusters have been obtained since the first one was reported in 2002. Recently, the sulfide-based T6 cluster was obtained, which is the biggest one in Tn series of clusters so far.11 However, for selenide-based Tn clusters, the largest one is T4,9, 12-13 which to some extent limits the structural diversity of cluster-based selenides.2, 14-15 Expanding the family of cluster-based open-framework metal selenides is very meaningful, but still challenging. During the decades in pursuing novel 3D metal selenide open frameworks composed by interconnection of supertetralhedral clusters (Tn, Pn and Cn clusters), only a limited number of achievements were reported, including (Bmmim)8[In8Sn8Se30(Se4)2](T2,2), OCF-1-ZnGaSe-TMDP (T4), OCF-6-GaSe-TMDP (T3), OCF-13-GaSe-TMDP (T3), UCR-7-InSe-TETA (T3), and OCF-42ZnGa(Ge/Sn)Se-TMDP (T2-T4), etc.8, 12-13, 16-21 It is well known that the protonated organic amines, serving as structure-directing agents (SDAs) and counter ions, play important roles in affecting crystallization of metal chalcogenide clusters. We have proved that the combination of indium and selenium with piperidine is a fruitful method to obtain a new family of selenide frameworks, known as one group of chalcogenide semiconductor zeolites (CSZ). The SBUs in so far reported selenidebased CSZs are tetrahedral T2 and/or P1 clusters, which are assembled into zeolite-type topological frameworks, such as BOR, SOD and C3N4.7, 9 Herein, we enrich the family members of cluster-based metal selenides and report three In-Se open frameworks

with

the

formula

of

[µ3-Se4]3.27·[In49.88Se95.92]·(C5H12N)26.0·(C2H8N)42.4

(1),

[In4Se10]·(C7H16N)1.8·(C2H8N)2.2 (2) and [In20Se39]·(C6H14N)12 (3), respectively (See supporting


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information for the detail synthetic method). Interestingly, the SBUs in all three compounds are connected by polyselenides (Sen2-, n = 3, 4). It is worth noting that the dendritic Se4 fragment, which usually exists stably in some small molecules with the protection by aryl rings or halogen atoms via intramolecular covalent bonds,22-24 is successfully stabilized in compound 1 and leads to the formation of a unique 3D In-Se open framework. In addition, such cases demonstrate that there are big potentials in developing flexible assembly of metal selenides via polyselenide linkers. The structure and composition of compound 1, 2 and 3 were characterized by single-crystal X-ray diffraction (SCXRD), elemental analysis (EA) and energy dispersive X-ray spectroscopy (EDS) (Figure S1). Their phase purity as well as solid-state stability was identified by powder X-ray diffraction (PXRD) and thermal gravimetric analysis (TGA), respectively (Figure S2-S5). Singlecrystal structure refinement indicates that compound 1, 2, and 3 crystallize in the space group R-3/c, Pnma, and P21/c, respectively (Table S1). In the framework of 1, each T2 cluster ([In4Se10]8-) is connected to other three T2 clusters via corer-sharing mode and the fourth corner is bonded to triangularly-shaped µ3-Se42- or µ3-T1 bridge (Figure 1a). The existence of µ3-Se42- in compound 1is further proofed by Raman spectra (Figure S6), in which, the wide band in the range of 262-277cm-1 could be attributed to the Se-Se bonds of µ3Se42-.25-26 The bond lengths of Se-Se (2.43 Å) in µ3-Se42- and In-Se (2.66 Å) in µ3-T1 are acceptable, which are coincident with the reported values.27-30 The ratio of µ3-Se42- and µ3-T1, locating at the same position (Figure S7), is about 1.25:1, which was obtained by structural refinement and further confirmed by EDS and EA analysis.


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Figure 1. Structure diagrams of compound 1. (a) one T2 cluster connects to three T2 clusters and one µ3-Se42- linker or µ3-T1 (left) and one µ3-bridge connects to three T2 clusters (right); (b) three kinds of windows; (c) compressed cage α with six windows A and six windows B; (d) adamantane cage β with three windows B and one window C; (e) 3D zeolitic framework; (f) the simplified 3,4connected net. Each µ3-bridge (µ3-Se42- or µ3-T1) is connected to three T2 clusters through sharing with corner Se atoms (Figure 1a). The co-assembly of triangularly-shaped Se42- or µ3-T1 with T2 clusters results in three kinds of windows: window A contains four T2 clusters and two µ3-bridges with the aperture of about 9.631×12.696 Å (measured between atomic centers); window B is composed by five T2 clusters and one µ3-bridge (aperture: 14.251 × 8.531 Å); window C is constructed by six T2 clusters


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to form regular ring with a largest aperture of about 14.240×14.240 Å (Figure 1b and Figure S8). Six windows A fuse together with six windows B to form an oblate cage α, and three windows B and one window C fuse together to form a hemispheric cage β (Figure 1c and 1d). The connectivity between cage α and cage β leads to a complex 3D net, in which cage α is surrounded by six cages β in ab plane and two cages β in c-axis direction (Figure 1e and Figure S9d). In contrast, cage β is surrounded by three cages α and three cages β in ab plane and one cage α and one cage β in the caxis direction (Figure S9e and S9f). If all T2 cluster and µ3-bridge are treated as pseudo-atoms (Figure S9a), the framework of 1 could be simplified into a novel (3, 4)-connected topology (Figure 1f). In this simplified net, 4-connected pseudo-atoms are derived from T2 clusters, and 3-connected pseudo-atoms are derived from µ3-Se42/ µ3-T1 bridges. This (3, 4)-connected net can be regarded as interrupted diamond topology, where cage α could be regarded as the fusion of six adamantane cages with a shared edge missing (Figure S9b and S9c). It is well known that the µ3-Q2- (Q=Se or S) fragments are rarely used as bridging units in the cluster-based chalcogenide frameworks,31 let alone µ3-Q42-. To the best of knowledge, the µ3-Se42- unit in compound 1 is for the first time reported in cluster-based metal chalcogenide frameworks. The guest species (protonated organic amine molecules and solvents) within the cavities are disordered and their atomic accurate positions could not be determined by SCXRD. The extraframework void space, which is occupied by guest species, is around 59.3% as calculated by the program PLATON.32 For compound 2, each T2 cluster is connected at two corners through corner-shared Se2- bridges, and the other two corners are extended by catenarian µ2-Se32- polyselenide units (Figure 2a-2b and Figure S11). For compound 3, each T3 cluster is connected at three corners through corner-shared Se2- bridges and leaves the fourth corner bonded to catenarian µ2-Se42- bridge (Figure 2d). Each


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catenarian µ2-Se42- bridge unit connects to adjacent two T3 clusters through sharing corner Se atom from T3 clusters (Figure 2e). This connection mode is similar to that in UCR-18, where the fourth corner of T3-InS cluster is connected to adjacent T3-InS cluster through a µ2-S32- bridge.33 The Tn SBUs and polyselenide linkers in compound 2 and 3 are assembled to form diamond-type topological frameworks with distorted adamantane cages. For compound 2, six catenarian µ2-Se32units are combined with ten T2 clusters to produce squashed adamantane cage (Figure 2c), while three catenarian µ2-Se42- units together with ten T3 clusters lead to the elongated adamantane cage in 3 (Figure 2f and Figure S12). The extra-framework space of compound 2 and 3 are calculated to be 18.0 % and 59.1 %, respectively, by the PLATON program.32

Figure 2. Structure diagrams of compound 2: (a) one T2 cluster connects to two T2 clusters and two µ2-Se32- bridges; (b) one µ2-Se32- bridge connects to two T2 clusters; (c) squashed adamantane cage


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constructed by T2 clusters and µ2-Se32- bridges. Structure diagrams of compound 3: (d) one T3 cluster connects to three T3 clusters and one µ2-Se42- bridge; (e) one µ2-Se42- bridge connects to adjacent two T3 clusters; (f) the elongated adamantane cage based on T3 clusters and µ2-Se42bridges. The ion-exchanging experiments were carried out by replacing protonated amines with cesium ions (see the Supporting Information for the detailed procedures). PXRD patterns of ion-exchanged samples suggest that compound 1 and compound 3 kept their original crystalline structure while compound 2 collapsed after ion exchange for 24 hours at room temperature (Figure S13). The results of elements analysis indicated that 100% and 90.3% of protonated amine molecules can be exchanged out by Cs+ ions in compound 1 and compound 3, respectively (Table S2). The optical band gap of the title compounds was investigated. As presented in Figure 3a, compound 1, 2, and 3 have band gap of around 2.19, 1.82, and 1.89 eV, respectively. We also investigated the photoelectric response properties of compound 1-3 in a photoelectrochemical cell with a three-electrode setup (Figure 3b-3d, also see more details in the Supporting Information). Under 0.6 V biased potential, the title compound modified photo-electrodes could present good photocurrent responses, indicating that these three In-Se compounds could be used as candidates in the applications of solar energy conversion.


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Figure 3. (a) Tauc plots of compound 1, 2 and 3 derived from UV-vis diffuse reflectance spectra. (bd) Photoelectric response versus time curves (J–t) of compound 1, 2 and 3, measured at applied potential 0.6 V. In conclusion, three supertetrahedral clusters-based In-Se open frameworks were synthesized via solvothermal method. These metal selenides were built from the co-assembly of supertetrahedral clusters and polyselenide linkers. Interestingly, a triangularly-shaped µ2-Se42- linker was for the first time stabilized in the inorganic framework without any protecting organic groups. Compound 1 and compound 3 exhibited good performance in ion exchange. In addition, all of these compounds exhibit narrow band gaps, which extend their potential applications in the field of photoelectronics. ASSOCIATED CONTENT Supporting Information


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The Supporting Information is available free of charge on the ACS Publications website at DOI: XXX General methods, tables for the results of single crystal data and elemental analysis, extra figures, powder X-ray diffraction. X-ray data in CIF format (CIF). Accession Codes CCDC 1565695 (Compound 1), 1565694 (Compound 2) and 1565696 (Compound 3) contain the supplementary crystallographic data for this paper. These data can be obtained free of e-mailing [email protected], or by contacting The Cambrige Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, U.K.; fax: +44 1223 336033. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] Notes The authors declare no competing financial interests. ACKNOWLEDGMENT We acknowledge National Natural Science Foundation of China (No. 21671142), Jiangsu Province Natural Science Fund for Distinguished Young Scholars (BK20160006), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD). REFERENCES


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For Table of Contents Use Only Supertetrahedral Cluster-Based In-Se Open Frameworks with Unique Polyselenide Ion as Linker Chaozhuang Xue, Jian Lin, Huajun Yang, Wei Wang, Xiang Wang, Dandan Hu, Tao Wu* College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China.

Three supertetrahedral Tn (n = 2, 3) clusters based chalcogenides are connected via polyselenide ligands to form the interrupted or elongated diamond-type frameworks.


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