Assembly of Oxygen-Stuffed Supertetrahedral T3-SnOS Clusters into

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Assembly of Oxygen-Stuffed Supertetrahedral T3-SnOS Clusters into Open Frameworks with Single Sn2+ Ion as Linker Jing Lv, Wei Wang, Li Zhang, Chaozhuang Xue, Dandan Hu, and Tao Wu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00727 • Publication Date (Web): 30 Jul 2018 Downloaded from http://pubs.acs.org on July 30, 2018

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Crystal Growth & Design

Assembly of Oxygen-Stuffed Supertetrahedral T3-SnOS Clusters into Open Frameworks with Single Sn2+ Ion as Linker Jing Lv, Wei Wang, Li Zhang, Chaozhuang Xue, Dandan Hu, and Tao Wu* College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China.

ABSTRACT: Here reported are three new types of cluster-based tin oxysulfides. Single-crystal Xray diffraction analysis reveals that both compound 1 [Sn]2[Sn40O16S74](DMA)4(DEA)10(H+DEA)12(H2O)20

(DMA

=

dimethylamine,

DEA

=

diethylamine)

and

compound

3

[Sn][Sn40O16S74](H+-DMA)12(DEA)4(H22+-DACH)3(H2O)20 (DACH = 1,2-diaminocyclohexane) are built from oxygen-stuffed supertetrahedral T3-SnOS clusters with corner-sharing S2- and single Sn2+ ion as bridging linkers, and compound 2 [Sn40O16S73](DMA)(H+-TMA)18(H2O)14 (TMA = trimethylamine) is constructed by the interrupted super-supertetrahedral T3,2 clusters. Such variable and unique linkage modes are very useful for constructing other type of cluster-based crystalline open-framework chalcogenides. In addition, compound 2 is the first case that displays photoluminescence emission among T3-SnOS-based chalcogenides.

Cluster-based metal chalcogenide materials have attracted extensive attention because they may potentially exhibit good performance in the application of photocatalysis due to the integration of porosity and semiconducting property, compared to the dense-phase chalcogenide materials.1-6 Experientially speaking, the size, composition, and assembly mode of clusters are closely related to the properties of the targeted open-framework materials.7-8 So far, two basic and useful strategies

ACS Paragon Plus Environment

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have been adopted to tune the properties of cluster-based metal chalcogenides. One is to build variable clusters with different size, shape and composition, and the other is to control the assembly mode for targeting open frameworks with tunable porosity.9-11 Tetrahedrally-shaped clusters (Tn, Pn, Cn, Tp,q) have been widely applied as the secondary building units (SBUs) to build the cluster-based metal chalcogenides.12 Among them, the structurally well-defined Tn clusters are good candidates for building multifunctional open-framework materials via the corner-sharing covalent assembly mode.7 So far, most studies are focused on construction of Tn clusters. By introducing low-valent tetrahedrally-coordinated metal cations into high-valence tetrahedrally-coordinated metal systems, the large-sized clusters, such as T4, T5 and T6, have been successfully obtained.13-15 It is worth noting that T6 cluster ([Zn25In31S84]25-) was recently reported as the largest known supertetrahedral cluster by our group.16 Metal chalcogenide clusters described above have proved to be good candidates for building a variety of novel structures via variable assembly modes, and the resulting structural topology of open-framework chalcogenides is determined by the connection mode between adjacent inorganic clusters.8, 10, 12 So far, the commonly observed case is the corner sharing mode by bi-coordinated µ2-S2-, through which the chalcogenide atoms at the vertex of clusters are shared each other to form multi-dimensional structures.7, 13-14, 17-18 In fact, some unique connection modes were ever reported before. For examples, the bi-coordinated sharing mode with the polysulfide chain as linker was observed in UCR-18,7 the co-existence of bicoordinated and tri-coordinated bridging S2- was firstly reported in OCF-89,19 and tetra-coordinated corner-sharing mode and vertex-edge connection mode were also existed in CIS-27.20 In addition, transition metal chelates and some N-containing organic ligands (such as imidazolate and bipyridine) can also serve as linkers to connect the adjacent clusters, in which N-donor organic ligands are bonded to the vertex of clusters.21-23 So far, the cases with metal ions as bridging units are very rare.


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Kanatzidis’s group found that Pt ions can assembly clusters into highly porous semiconducting gels.24 Huang's group reported that [SbS3] units can be used to bridge T2 clusters.25 Herein, we report three new tin oxysulfide open frameworks with the framework formula of [Sn]2[Sn40O16S74] (1), [Sn40O16S73] (2) and [Sn][Sn40O16S74] (3), respectively. Notably, all three compounds are built with the same SBUs of oxygen-stuffed supertetrahedral T3-SnOS clusters. Interestingly, they display different assembling structure via different bridging units and linkage modes, especially for compound 1 and compound 3 with unique type of single µ2-Sn2+ and µ3-Sn2+ ion as linker, respectively, which have never been observed before. In addition, the interrupted supersupertetrahedron T3,2-SnOS clusters are also observed in compounds 2 and 3. Compounds 1-3 were synthesized under solvothermal condition. The crystallization process of products was very sensitive to the reaction temperature. No targeted products could be obtained when the reaction temperature is fluctuated over 10 °C. The empirical formula of compounds 1-3 were determined by single-crystal X-ray diffraction (SCXRD) analysis, elemental analysis (EA) of C/H/N, Fourier transforming-infrared spectrum (FT-IR), TGA and EDS measurements (Figure S1S5). The purity of the synthesized samples was also determined by powder XRD (Figure S6-8). Detailed crystallographic data and structure refinement parameters of compounds 1-3 were summarized in Table S1. Single-crystal X-ray diffraction analysis revealed that compound 1 crystallized in monoclinic system with space group of C2/c. The most prominent structure feature of 1 is that three of four apexes of each T3-SnOS cluster are covalently bonded to the adjacent T3-SnOS clusters via cornersharing µ2-S2- site, and the remaining fourth one is connected to another T3-SnOS cluster through a single µ2-Sn2+ ion as linker (Figure 1a-1b). Compared to an ideal supertetrahedral T3-SnS cluster


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with the formula of [Sn10S20], the unique T3-SnOS cluster is constructed by stuffing one oxygen atom into each adamantane cage in T3-SnS cluster. X-ray photoelectron spectroscopy analysis demonstrated the coexistence of two different peaks for Sn components, which can be assigned to Sn2+ and Sn4+, respectively (Figure S9).26 To the best of our knowledge, this is the first case of T3SnOS cluster-based chalcogenides containing the mixed valence of Sn2+ and Sn4+. Finally, the adjacent T3-SnOS clusters are assembled via corner-sharing µ2-S2- and/or single µ2-Sn2+ ions into 3D anionic open framework with two-fold interpenetrated diamond topology (Figure S10). Interestingly, a distorted adamantane cage is formed via the assembly of two µ2-Sn2+ sites and ten T3-SnOS clusters. In this cage, there are two types of six-membered ring composed of T3-SnOS clusters: one is built from six T3-SnOS clusters via corner-sharing µ2-S2-, the other is built from six T3-SnOS clusters via four corner-sharing µ2-S2- and two µ2-Sn2+ sites (Figure 1c). Such connection mode is similar to [Sn5S9O2] with the cristobalite-type topology, except that the part of µ2-S2- linkers are replaced by µ2-Sn2+ linkers (Figure S11).27 In [Sn5S9O2], each T3-SnOS cluster is connected by corner-sharing µ2-S2-sites, and the Sn-S-S angle is around 113.1°. As the distance between the adjacent T3-SnOS clusters is increased by the µ2-Sn2+ linker, the extra-framework space (occupied by organic amine and solvents) in 1 (46.6 %) is much larger than that of [Sn5S9O2] (10.2 %), calculated by the PLATON program.19


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Figure 1. (a) One T3-SnOS cluster connects to four T3-SnOS clusters via three µ2-S2- and one µ2Sn2+ linker in compound 1; (b) one µ2-Sn2+ linker connects to adjacent two T3-SnOS clusters; (c) the adamantane cage based on T3-SnOS clusters and µ2-Sn2+ linkers. Compound 2 crystallized in monoclinic system with the space group of P21/n. It is also built from T3-SnOS clusters via corner-sharing µ2-S2- linkers. We notice that half of T3-SnOS clusters in 2 are connected to adjacent four T3-SnOS clusters, and the remaining T3 clusters adopt three-connection mode to bond three T3 clusters via corner-sharing µ2-S2- linkers, which are named as µ4-T3 (Figure 2a) and µ3-T3 (Figure 2b), respectively. Interestingly, four T3-SnOS clusters are co-assembled into one interrupted super-supertetrahedron T3,2 clusters. Such interrupted T3,2 clusters are connected each other by corner-sharing mode to form a 4-connected 2D (4, 4) layer (Figure 2d). The structure of 2 is similar with OCF-61 with the framework formula of [Sn42O16Se77]18-, in which [Sn2Se6]4− units occupy the interruption sites in the interrupted T3,2 cluster in 2 (Figure S12).28


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Figure 2. (a) One µ4-T3 cluster connects to four T3 clusters via corner-sharing µ2-S2- linkers in 2; (b) one µ3-T3 cluster connects to three T3 clusters via corner-sharing µ2-S2- linkers in 2 and 3; (c) one µ4T3 cluster connects to four T3 clusters via three corner-sharing µ2-S2- linkers and one µ3-Sn2+ bridge in 3; (d) two-dimensional (4, 4)-grid layer assembled by the interrupted T3,2 clusters in 2; (e) the polyhedral connectivity model of eight adjacent interrupted T3,2 cluster clusters in 3. Compound 3 crystallized in monoclinic system with the space group of P21/m. It is assembled by T3-SnOS clusters via two types of linkage modes, i.e. corner-sharing µ2-S2- and µ3-Sn2+. Two µ4-T3 clusters are fused with another two µ3-T3 clusters to form an interrupted T3,2 cluster (Figure 2b and 2c). The edge lengths of the interrupted T3,2 cluster are in the range of 21.8091-25.3286 Å. Compared with the regular super-supertetrahedral T3,2 cluster in SOF-2 with composition of In-SnS,29 the size of nanocage (represented by a yellow standard sphere) at the center of the interrupted T3,2 cluster in 3 is around 4.0 Å, which is smaller than that (4.7 Å) of T3,2 cluster in SOF-2 (Figure S13). Each interrupted T3,2 cluster is connected with another interrupted T3,2 cluster by sharing four terminal µ2-S2- and two µ3-Sn2+ ions. When each interrupted T3,2 cluster is treated as a 6-connected node, the structure of 3 can be simplified to a two-fold interpenetrated PCU-type topology, as shown in Figure S14.


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Figure 3. Tauc plots of compounds 1-3 derived from UV-vis diffuse-reflectance spectra.


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Figure 4. (a) The photoluminescence excitation and emission spectra of compound 2; (b) PL spectra of compound 2 at different temperature; (c) PL decay curves of compound 2 tested at emission wavelength of 555 nm. The inset shows the temperature-dependent PL lifetime.


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To determine the optical band gap of as-synthesized compounds 1-3, UV-vis absorption measurements were performed, as displayed in Figure 3. The band gap of compounds 1-3 was determined to be 3.12 eV, 3.03 eV and 2.81 eV, respectively, from the extrapolation of the linear part in the plot of [F(R)hv]2 vs energy. Generally, tin oxysulfides have better semiconducting properties compared to pure tin oxides. The photoluminescence property of these compounds was also investigated. To be noticed, upon the excitation at 505 nm, compound 2 exhibits a maximum emission peak at 555 nm at room temperature (Figure 4a). The emission peak is insensitive to temperature although PL intensity increases with the temperature decreasing (Figure 4b). The average lifetime was determined by the expression of τave = ∑Aiτi2/∑Aiτi. Figure 4c shows the decay curve of the 555 nm emission for compound 2 at different temperature. Fitting the decay curves by a tri-exponential can give the average decay lifetime of 1.66 ns at room temperature and 6.94 ns at 23 K. PL lifetime of compound 2 increases with the temperature decreasing (Table S2). Unfortunately, no fluorescence peak was observed in compounds 1 and 3. The photoluminescence mechanism of 2 is still not clear now. However, according to the literature,30-33 we tentatively propose that the fluorescence of compound 2 may be associated with the crystal defects induced by crystal growth since the PL quantum yield from different batches of 2 is inconsistent (Figure S15). In conclusion, three tin oxysulfide open frameworks were constructed by supertetrahedral T3SnOS clusters. Compound 1 and compound 3 enriched the connectivity complexity of T3-SnOSbased architecture by introducing single Sn2+ ion as linker. In addition, compound 2 composed of the interrupted super-supertetrahedral T3,2 clusters is the first case displaying photoluminescence property among T3-SnOS-based chalcogenides.


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ASSOCIATED CONTENT Supporting Information 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 patterns (PDF) Accession Codes CCDC 1840076 (Compound 1), 1838618 (Compound 2) and 1838619 (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).


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For Table of Contents Use Only Assembly of Oxygen-Stuffed Supertetrahedral T3-SnOS Clusters into Open Frameworks with Single Sn2+ Ion as Linker Jing Lv, Wei Wang, Li Zhang, Chaozhuang Xue, Dandan Hu, and Tao Wu* College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China.

The oxygen-stuffed supertetrahedral T3-SnOS clusters are assembled into three different open frameworks via corner-sharing µ2-S2-, single µ2-Sn2+ and µ3-Sn2+ linkers.


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Assembly of Oxygen-Stuffed Supertetrahedral T3-SnOS Clusters into

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