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Article Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

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Hybrid Assembly of Different-Sized Supertetrahedral Clusters into a Unique Non-Interpenetrated Mn−In−S Open Framework with Large Cavity Hongxiang Wang,†,⊥ Wei Wang,†,⊥ Dandan Hu,† Min Luo,† Chaozhuang Xue,† Dongsheng Li,‡ and Tao Wu*,† †

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang, Hubei 443002, China

‡

S Supporting Information *

ABSTRACT: Reported here is a unique crystalline semiconductor openframework material built from the large-sized supertetrahedral T4 and T5 clusters with the Mn−In−S compositions. The hybrid assembly between T4 and T5 clusters by sharing terminal μ2-S2− is for the first time observed among the cluster-based chalcogenide open frameworks. Such threedimensional structure displays non-interpenetrated diamond-type topology with extra-large nonframework volume of 82%. Moreover, ion exchange, CO2 adsorption, as well as photoluminescence properties of the title compound are also investigated.

1. INTRODUCTION In recent years, chalcogenide-based open-framework materials have aroused great interests due to their characteristics in the integration of porosity and semiconducting property.1−7 Compared to the traditional insulated oxide-based zeolites, chalcogenide-based open-framework crystalline semiconductor materials represent more diversity in their extended applications, such as photoelectric response, photoluminescence, electrocatalysis, and photodegradation, besides ion exchange and gas adsorption.8−14 Various functionalities of such openframework materials are largely dependent on the size and type of the secondary building units (SBUs). Great efforts have been devoted to designing and creating novel SBUs, which are useful for predicting the final topological structures and simultaneously introducing some specified functionality. Various metal chalcogenide supertetrahedral clusters with regular geometric shape were developed as SBUs, including basic-(Tn), hierarchical-(Tp,q), penta-(Pn) and capped-(Cn) forms.15−20 Among them, the basic supertetrahedral chalcogenide Tn clusters (n indicates the number of metal sites along the edge of tetrahedron, n = 2−6 currently), regarded as the structural fragments of cubic ZnS-type semiconductors, are the most commonly used types in construction of cluster-based chalcogenide open frameworks. As a result of the assembly of Tn clusters, a large amount of 4-connected nets (such as ABW, SOD, BCT, NAB, and quartz)21−26 and 3,4-connected nets (such as boracite and C3N4)19,27−29 have been established by © XXXX American Chemical Society

sharing the terminal chalcogen atoms. Thus far, the majority of the reported cluster-based metal chalcogenide open frameworks are built from the same type and the same size of tetrahedral clusters, and only a few cases were constructed by the hybrid assembly of different type and size of tetrahedral clusters, which lead to the hybrid linkage between adjacent clusters, such as T2-P1, T2-T3, T2-T4, T3-T4, and T3-T5 (Table S1).22,30−33 However, the assembly of large-sized clusters with the hybrid linkage of T4-T5 has never been reported before. In addition, the functionality of chalcogenide-based openframework materials is to large extent dependent on the pore accessibility. However, there is a serious issue in such clusterbased chalcogenide frameworks; that is, the effective void spaces are dramatically reduced due to the unhappy blockage caused by the different degree of interpenetration, especially in the system of centrosymmetric diamond-type nets.1,25,34,35 As a result of the interpenetration, the low nonframework volume inevitably restrains the applications of open frameworks in the field of host−guest chemistry. One of the feasible strategies on preventing the interpenetration is to realize (3,4)-connected net.36 Assembling small-sized clusters (P1, T2, and T3) into open frameworks is also an effective strategy to avoid net interpenetration (Table 1). However, the small-sized clusters do not facilitate the increase of the nonframework volume. Received: April 4, 2018

A

DOI: 10.1021/acs.inorgchem.8b00907 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Table 1. Pore Parameters of Several Cluster-Based Metal−Chalcogenide Open Frameworks compound 43

OCF-31 UCR-2121 ICF-2123 OCF-640 ASU-3424 UCR-134 UCR-522 CdInS-4425 OCF-544 ICF-523 SCIF-843 SCIF-943 UCR-1533 UCR-1735 OCF-45 a

formula 6−

[In8S15] [Ga3.3Ge0.7S8]3.3− [In4Se8]4− [Ga10Se18]6− [In10S18]6− [Zn4In16S33]10− [Zn4Ga16S33]10− [Cd4In16S33]10− [Zn4Ga16Se33]10− [Zn4In16S33]10− [In16Cd4S31(L1))2]8− b [In16Cd4S31(L2)2]8− c [In44S72]12− [Cu5In30S54]13− [Mn11In43S87]23−

SBU

interpenetration

window aperture (Å)

cluster size

ex. vol.a

topology

P1 T2 T2 T3 T3 T4 T4 T4 T4 T4 T4 T4 T3, T5 T5 T4, T5

no no no no no no yes yes yes yes yes yes yes yes no

11.2 × 24.2 8.0 × 14.5 8.2 × 16.2 12.3 × 22.7 11.8 × 23.6 15.3 × 16.4 16.0 × 26.0 16.5 × 31.3 16.7 × 30.3 15.9 × 31.3 25.2 × 34.8 17.3 × 33.3 18.2 × 31.2 21.4 × 38.6 19.6 × 35.2

10.8 Å 7.5 Å 8.2 Å 11.5 Å 11.7 Å 15.3 Å 14.6 Å 15.8 Å 15.5 Å 15.8 Å 14.9 Å 15.1 Å 11.7 Å, 19.7 Å 19.6 Å 15.7 Å, 19.6 Å

69.4% 58.6% 56.7% 74.0% 70.0% 63.0% 56.0% 58.4% 56.9% 56.3% 65.0% 61.6% 58.3% 67.1% 81.7%

SD SD SD SD SD DD DD DD DD DD DD DD DD SD

ex. vol. = extra-framework volume. bL1 = 2-ethylimidazolate. cL2 = 5,6-dimethyl-benzimidazolate; SD = single diamond; DD = double diamond. in the void space of the framework cannot be identified owing to their serious disorder. The SQUEEZR subroutine in PLATON was applied.42 2.4. Powder X-ray Diffraction. Powder X-ray diffraction (PXRD) data were collected on a desktop diffractometer (D2 PHASER, Bruker, Germany) using Cu Kα (λ = 1.540 56 Å) radiation operated at 30 kV and 10 mA. The experimental PXRD and the simulated one from single-crystal structure of OCF-45 are shown in Figure S1. 2.5. Elemental Analysis. Energy-dispersive spectroscopy (EDS) analysis was performed on scanning electron microscope (SEM) equipped with EDS detector. An accelerating voltage of 25 kV and 40 s accumulation time were applied. EDS results clearly confirmed the presence of In, Mn, and S elements (Figure S2). Elemental analysis of C, H, and N was performed on VARIDEL III elemental analyzer for pure OCF-45 Calcd. (wt %): C, 17.52; N, 4.514; H, 3.101; found: C, 16.53; N, 4.618; H, 3.228. The In/Mn ratio was determined by inductively coupled plasma atomic emission spectroscopy mass spectrometer (ICP-AES, on Leeman’s PROFILE SPEC spectrometer): In/Mn = 3.89. 2.6. Thermogravimetric Measurement. A Shimadzu TGA-50 thermal analyzer was used to measure the thermogravimetric (TG) curve by heating the sample from room temperature to 800 °C with heating rate of 5 °C/min under N2 flow. The weight loss of the first step could be ascribed to the weight loss of disordered H2O; the second and third steps involved the loss of two template amines together with H2S gas (Figure S3). 2.7. UV−Vis Absorption Measurement. Room-temperature solid-state UV−vis diffusion reflectance spectra of crystalline samples were measured on a Shimadzu UV-3600 UV−vis-NIR spectrophotometer (NIR = near-infrared) coupled with an integrating sphere by using BaSO4 powder as the reflectance reference. The absorption spectra were calculated from reflectance spectra by using the Kubelka− Munk function: F(R) = α/S = (1 − R)2/2R, where R, α, and S are the reflection, the absorption, and the scattering coefficient, respectively. The band gap is estimated to be 2.7 eV (Figure S4). 2.8. Fourier Transform Infrared Absorption. Fourier transform infrared (FTIR) spectra were performed on a Thermo-Nicolet Avatar 6700 FT-IR spectrometer with cesium iodide optics allowing the instrument to observe from 500 to 4000 cm−1. The result and analysis of attributions of peaks are shown in Figure S5. 2.9. Ion Exchange Experiment. The protonated organic amines in the external framework can be exchanged out by Cs+ ions. Typically, 10 mg of crystalline sample of OCF-45 was added into 10 mL of CsCl aqueous solution with different concentrations (0.1 and 1 M) in the glass vials at different temperatures (25, 60, and 85 °C). Such process was maintained for 12 h to make the exchange completely. The ionexchanged samples were washed three times by deionized water and then filtered off.

Therefore, using the large and different-sized clusters to build chalcogenide open frameworks is desirable, since they can potentially avoid interpenetration and increase nonframework volume.21,24,37−41 Herein, we report a unique non-interpenetrated Mn−In−S open framework built from supertetrahedral T4 and T5 clusters via hybrid linkage. The title compound has the formula of [(In43Mn11S87)]·12(H+-DBU)·11(H+-PR)·5.1H2O (denoted as OCF-45-MnInS, OCF = organically directed chalcogenide framework, DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene, and PR = piperidine). Such open framework with large nonframework volume of 82% is realized through the connection of two largesized clusters by sharing terminal μ2-S2−. This open framework has a single diamond-type net when T4 and T5 clusters are considered as nodes. Notably, it is the first case of cluster-based chalcogenide framework built from two large-sized clusters. In addition, ion exchange, CO2 adsorption, and Mn2+-related photoluminescence of such material were also investigated.

2. EXPERIMENTAL SECTION 2.1. Materials. Sulfur powder (S, 99.99%, metal basis), Mn(Ac)2· 4H2O (analytical reagent (AR), 99.99%, metal basis), indium powder (In, AR, 99.99%, 200 mesh), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 98%), piperidine (PR, ≥99.0%, liquid), and deionized water. All reagents used here are commercially available and without further purification. 2.2. Synthesis of OCF-45-MnInS. A mixture of indium powder (115.0 mg, 1 mmol), sulfur powder (60 mg, 1.88 mmol), Mn(Ac)2· 4H2O (47 mg, 0.19 mmol), PR (1.0 mL), 1,8-diazabicyclo[5.4.0] undec-7-ene (0.5 mL), and H2O (1.0 mL) was prepared and stirred in a 23 mL Teflon-lined stainless steel autoclave for 20 min. The vessel was sealed and heated at 200 °C for 6 d, and the autoclave was naturally cooled to room temperature. Orange octahedral-like crystals were obtained with a few impurities. The raw products were purified by hand and washed three times by ethanol, filtered off, and further purified by hand with a yield of 62.2 mg (17.3% based on Mn(Ac)2· 4H2O). 2.3. Single-Crystal Structure Characterization. Single-crystal X-ray diffraction measurements were performed on Bruker Photon II CPAD diffractometer with graphite monochromated Mo Kα (λ = 0.710 73 Å) radiation at 120 K. The structure was solved by direct method using SHELXS-2014, and the refinement against all reflections was performed by using SHELXL-2014. The data collection and refinement parameters for OCF-45 are summarized in Table S2. All the protonated organic amine molecules and solvent molecules located B

DOI: 10.1021/acs.inorgchem.8b00907 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

were ever observed in other T5 clusters, such as [In34S56]10− in UCR-1533 and [In28Cd6S56]18− in ISC-10-CdInS.6,45 Another intriguing characteristic of OCF-45 is the large window apertures and large extra-framework volume. As shown in Figure 2a, a large triangle window (27-membered ring if only

2.10. Gas Adsorption. The N2 and CO2 adsorption isotherms of cation-exchanged samples were recorded using a Micromeritics ASAP 2020 physisorption analyzer. The cation-exchanged samples were dried in the vacuum oven for 4 h and were further degassed for 10 h at 333 K. N2 adsorption isotherm was recorded at 77 K. CO2 adsorption isotherms were recorded at 195, 273, and 298 K, and the temperature of the experiments was controlled by a Dewar flask. 2.11. Photoluminescence (PL) and Photoluminescence Excitation (PLE) Spectra. PL and PLE spectra were recorded by an HORIBA scientific Fluorolog-3 steady-state and time-resolved fluorescence spectrophotometer equipped with a 450 W xenon lamp. PL decays were recorded using an HORIBA scientific Fluorolog-3 steady-state fluorimeter with a time-correlated single-photon counting (TCSPC) spectrometer and a pulsed xenon lamp as the excitation source. Low-temperature PL spectra were recorded on an HORIBA scientific Fluorolog-3 spectrophotometer with a low-temperature accessory. 2.12. PL Dynamics. The time-correlated single photon-counting (TCSPC) experiments were performed, and all time-dependent PL curves were fitted to a multiexponential function of I(t) = ∑Ai exp(−t/τi). The average lifetimes are determined by the expression of τave = ∑Aiτi2/∑Aiτi.

3. RESULTS AND DISCUSSION 3.1. Single-Crystal Structure of OCF-45. Structurally, the most prominent feature of OCF-45 is the hybrid assembly of supertetrahedral T4 and T5 cluster. It is well-known that lowvalent transition-metal cations (like Cu+, Zn2+, Fe2+, and Mn2+) play a vital role in increasing the size of supertetrahedral Tn clusters due to the requirement of local charge balance.15,16 μ4S2− sites, appearing in T4 or larger Tn clusters, cannot be balanced by four trivalent or tetravalent metal ions according to the Pauling’s electrostatic rules. Therefore, T2 and T3 cluster could be obtained when trivalent or tetravalent metal ions are only adopted. The combination of trivalent or tetravalent metal ions with monovalent or divalent metal ions could give rise to the formation of T4, T5, and T6 clusters. Along with such methodology, both Mn2+ and In3+ ions are used to build OCF45 here. Unexpectedly, T4-MnInS cluster as well as T5-MnInS cluster appears in the framework of OCF-45 through hybrid coassembly mode. As shown in Figure 1, T5-MnInS cluster is

Figure 2. (a) Large 27-membered ring channel built from three T4 clusters and three T5 clusters; (b) three-dimensional open-framework structure of OCF-45 with single diamond net, orange cluster: T4MnInS, indigo one: T5-MnInS.

considering metal sites) with the edge of 31.51 and 35.19 Å is built by the connection of three T4 clusters and three T5 clusters. When each T4 and T5 cluster is considered as node, the framework of OCF-45 can be simplified into a noninterpenetrated diamond-type net (Figure 2b and Figure S6). Such non-interpenetrated framework shows extra-large void space volume of 81.7% calculated by PLATON. It is noteworthy that the majority of metal-chalcogenide open frameworks based on T4 or T5 clusters, such as UCR-5, CdInS44, and UCR-17 (Table 1), usually adopt twofold interpenetration form, leading to ∼60% nonframework volume. There is only one unique example, UCR-1, which is built from T4 cluster and represents non-interpenetrated framework. However, it still has low nonframework volume of 63% due to the crowded arrangement of clusters. Therefore, OCF-45 built from different-sized T4 and T5 clusters by sharing terminal μ2-S2− is a rare case among the family of cluster-based metal chalcogenides. 3.2. Ion-Exchange Experiments. Ion-exchange experiments were performed to activate the micropore of OCF-45. As usual, the protonated organic amines, including H+-DBU and H+-PR, could be exchanged out easily by alkali metal ions (like Cs+), because cesium ions serving as typical soft acid show strong affinity to soft base of S2− species from the chalcogenide framework according to hard and soft acid−base (HSAB) theory. As demonstrated in Figure 3, the solid-state samples of OCF-45 retain their crystalline structure after Cs+-exchanging process, although the main diffraction peaks slightly shift to low angle, which demonstrates the shrinkage of framework when the large-sized amine templates are replaced by small-sized Cs+

Figure 1. Linkage mode between T4-MnInS and T5-MnInS cluster. (a) T5-MnInS cluster is connected with four T4 clusters and (b) vice versa.

surrounded by four T4-MnInS clusters by sharing the terminal μ2-S2− and vice versa. It is noteworthy that T5-MnInS cluster in OCF-45 is in the coreless form. The formula of T5-MnInS cluster is calculated to be [In27Mn7S56]17− according to singlecrystal diffraction and ICP-AES results, in which there are only 34 metal sites in the coreless cluster. Such special phenomena C

DOI: 10.1021/acs.inorgchem.8b00907 Inorg. Chem. XXXX, XXX, XXX−XXX

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terized by PXRD to confirm its structural integrity (Figure S10). 3.4. PL and PLE of OCF-45. The PL properties of TnMnInS-based domain or Mn-doped T5-CdInS domain were ever explored.6 Compared to typical Mn2+-doped II−VI semiconductor nanomaterials with Mn2+-related emission in the range of 580−600 nm, the cluster-based metal chalcogenides with Mn2+ dopants show a large red-shifted emission (greater than 620 nm).48,49 The Mn2+-related emission from such semiconductor materials is generally accepted to originate from a rapid energy transfer from host lattice of Tn clusters into Mn2+ d-orbital and subsequent 4T1 → 6A1 transition.2,6,48 The room-temperature PL) and PLE spectra of OCF-45 were investigated, as shown in Figure 5a. OCF-45 clearly exhibits

Figure 3. PXRD patterns of Cs+-exchanged samples obtained from Cs+ aqueous solution with different concentrations at different exchanging temperature.

ions. 90% of the protonated amines could be exchanged out by Cs+ ions at room temperature, and all amines in OCF-45 could be exchanged out at above 60 °C (Table S3). In fact, it is a very rare case to keep original structure after ion-exchange process among the reported cluster-based metal chalcogenide open frameworks. 3.3. Gas Adsorption. Compared with oxide-based zeolites, chalcogenide-based open frameworks have shown superior properties in the uptake of CO2 because of strong affinity between polarizable CO2 molecules and sulfide ions from the framework. However, only few crystalline chalcogenide open frameworks (RWY and CPM-120) and amorphous chalcogels (such as MoSx and CoMo3S13) are observed with the CO2 adsorption capabilities.11,46,47 CO2 adsorption isotherms for Cs@OCF-45 samples were performed at 195, 273, and 298 K (Figure 4). All three isotherms are well-fitted with dual-site

Figure 5. (a) PL and PLE spectra of OCF-45 at room temperature. (b) Temperature-dependent PL spectra of OCF-45.

several excitation peaks (383, 467, and 500 nm) at room temperature. The excitation band at 383 nm is attributed to the absorbed energy by host lattice, which undergoes energy transfer from clusters to Mn2+ ions in the T4 and T5 clusters. Other excitation bands are attributed to the direct energy absorption by Mn2+ ions. Under the excitation of 383 nm, an obvious broad PL emission at 633 nm was observed (Figure 5a and Figure S11). Besides, the temperature-dependent PL property of OCF-45 was also investigated. There is a large red-shift of 30 nm when the testing temperature is decreased from 293 to 23 K (Figure 5b). Such red-shift may be resulted from lattice strain in the asymmetric ligand field of Mn2+ ions at low temperature. Moreover, the decay lifetime of OCF-45 is measured at different temperatures upon excitation at 383 nm. Fitting the decay curves by a biexponential can give average decay lifetimes of 21 μs at room temperature and 1 ms at 23 K.

Figure 4. CO2 adsorption isotherms of Cs@OCF-45 at 195, 273, and 298 K, respectively.

Langmuir mode (Figure S7 and Table S4). By contrast, the CO2 uptake isotherms of original OCF-45 were also performed (Figure S8), which demonstrates that original sample of OCF45 is free of micropores. Unfortunately, no obvious N2 adsorption is observed for Cs@OCF-45 (Figure S9), which may be caused by the reason that the large molecular dynamic radius of N2, compared to CO2, cannot diffuse into the shrunk window apertures or pores in the ion-exchanged sample due to the blockage of a large amount of Cs+ ions. The Cs@OCF-45 sample after gas-adsorption experiment was further characD

DOI: 10.1021/acs.inorgchem.8b00907 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Notes

The lifetime of OCF-45 at 633 nm emission increased with the temperature decreasing (Figure 6 and Table S5).

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by 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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Figure 6. PL decay curve of OCF-45 under the excitation of pulsed 383 nm and emission wavelength of 633 nm at different temperature. (inset) The temperature-dependent PL lifetime.

4. CONCLUSION We report a unique crystalline semiconductor open framework built from metal chalcogenide supertetrahedral clusters with the different size of T4-MnInS and T5-MnInS. To the best of our knowledge, it is the first time to realize hybrid assembly of such large-sized clusters in the field of chalcogenide open frameworks. This structure displays a single diamond-type topology when considering each cluster as node. As a result of noninterpenetrated framework, OCF-45 also shows extra-large nonframework volume of 82%. Moreover, it also represents reversible ion exchange, CO2 adsorption, and Mn2+-related photoluminescence property.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b00907. Experimental details, SCXRD data and PXRD, elemental analysis, additional structural figures, UV−vis absorption spectra, IR spectra, TGA, as well as the details of ionexchange experiments (PDF) Accession Codes

CCDC 1829204 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 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

*E-mail: [email protected]. ORCID

Min Luo: 0000-0001-8080-0881 Dongsheng Li: 0000-0003-1283-6334 Tao Wu: 0000-0003-4443-1227 Author Contributions ⊥

These authors contributed equally. E

DOI: 10.1021/acs.inorgchem.8b00907 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

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DOI: 10.1021/acs.inorgchem.8b00907 Inorg. Chem. XXXX, XXX, XXX−XXX