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Heterometallic cluster-based indium-organic framework
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Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x With the help of the ligand-oriented method, we have successfully embedded independent copper-based units in indium-organic framework system for the first time, in which the Cu4I4 clusters and In3O(CO2)6 clusters coexist. This heterometallic cluster-based framework InOF-8 has a large porosity with extra-open channels along c-axis, and its sorption capacity has been also investigated.
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Among solid state porous materials, such as carbon-based materials, natural zeolites, covalent-organic materials (COFs) and metal-organic frameworks (MOFs), these MOF materials stand out for their well-refined structures and permanent porosity.1 Numerous experimental and theoretical researches have confirmed that MOF materials of high crystallinity turn out to be promising platform for carbon dioxide capture,2 hydrogen storage,3 hydrocarbon separation4 and drug delivery5 in the past decades. Therefore, it is of great importance for MOF chemists to design and synthesize novel multifunctional materials with various organic ligands and inorganic metal units, including single-metal-ion-based clusters and heterometallic clusters. Recently, post-synthetic method6 and transmetalation method,7 routes to obtain isoreticular MOF networks with preserved crystallinity and high surface area and structural features of the original frameworks, have been extensively utilized for the construction of MOF structures. However, these methods might not be always suitable and compatible for the well-studied porous indium-organic frameworks (InOFs). Experimentally speaking, In(III) ions are so COO--affinitive centers with high coordination numbers8 that people are more likely to select multicarboxylate ligands to prepare stable InOF materials, in which most of previously reported InOF crystals are only constructed from the combination of In(III) centers and the carboxylate ligands or functionalized carboxylate ligands, while heterometallic InOF structures or heterometallic cluster-based InOF structures are rarely seen. Very recently, we reported an interesting zinc-based MOF structure (FJI-3) on Chem. Commun., in which it simultaneously incorporated 4-connected Zn2(CO2)4 paddle wheels, topologically equivalent 6-connected Zn3O(CO2)6 trimer and Zn4O(CO2)6 secondary building units (SBUs), featuring a new hexanodal topology.9 In this case, the integration of typical single-metal-ionbased SBUs in one MOF structure has been also confirmed as a facile and ingenious method for synthesizing new InOF This journal is © The Royal Society of Chemistry [year]
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materials.10 Generally speaking, indium(III) ions tend to generate three types of SBU-based coordination frameworks throughout the literatures, namely, 8-coordinated In(CO2)4 monomers,11 infinite In(OH)(CO2)2 chains12 and 6-connected In3O(CO2)6 cluster trimers.13 Therefore, it is still a challenging task to obtain porous heterometallic InOF structures from these In(III)-based SUBs together with other metal building units. Our group has long been seeking to synthesize solid state porous materials particularly based on main group element In(III). Thinking outside the box, we has been innovatively embedded functional Cu(I)-based units in the InOF system for the first time. In our new perspective, by taking the bifunctional ligand-directed method, called Bifunctional Method, it is effective to construct InOF materials where COO--affinitive In(III) ions only bind to carboxylate groups while N-affinitive Cu(I)-based units only bind to pyridyl N-centers based on the bifunctional ligands. And in this work, we report one intriguing heterometallic cluster-based InOF structure: [(In3O)2(Cu4I4)3(nia)12(H2O)6][NO3)2]•Solvent (InOF-8, Hnia = nicotinic acid) based on two kinds of singlemetal-ion-based clusters, which comprises classic In3O(CO2)6 clusters and tetrahedral Cu4I4 clusters. Moreover, sorption behaviour of this desolvated InOF-8 material has been analyzed owing to its open pore environment, and its IAST calculation has also been conducted for their selectivity at low pressure region.
Fig. 1 a) Highlighted asymmetric unit of InOF-8 and the coordination environment of nia- ligand; tetrahedral Cu(I) centers and octahedral In(III) centers. b) 4-coordinated Cu(I)-based [Cu4I4N4] moiety. c) and d) 6coordinated In(III)-based [In3O(CO2)6] moiety.
[journal], [year], [vol], 00–00 | 1
ChemComm Accepted Manuscript
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Jinjie Qian,a,b Feilong Jiang,a Kongzhao Su,a,b Jie Pan,a,b Zhenzhen Xue,a,b Linfeng Liang,a,b Partha Pratim Bag,a and Maochun Hong*a
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For light yellow stick-like single crystals of InOF-8, they are successfully and solvothermally prepared by heating the mixture of In(NO3)3 salt, cuprous iodide salt and Hnia ligand in a 1:2:4 molar ratio in DMA/MeCN mixed solution (1:1, v/v; DMA = N,N'-diethylformamide; more detail please refer to the Section S1 in the Supporting Information) at 120 oC for one week. The phase purity of the microcrystal product has been confirmed by the powder X-ray diffraction (PXRD) analysis (Fig. S5). Then the resultant framework formula is defined as a positive [(In3O)2(Cu4I4)3(nia)12(H2O)6]2+ network which is calculated from the combination of thermogravimetric analysis (TGA) curve and elemental analysis (EA) data after the SQUEEZE process. It is revealed by single crystal X-ray diffraction analysis that InOF-8 is crystallized in the trigonal space group P6/mmc with cell parameters a = b = 21.9173(4) Å, c = 28.2685(4) Å, V = 11760.0(3) Å3 (refer to Table S1), and its asymmetric unit consists of half a In(III) ion, one quarter of Cu4I4 cluster, one nialigand, one sixth µ3-O2- anion and half a terminally coordinated water molecule as shown in Fig. 1a. In the coordination environment, through the way one pyridyl N atom to one Naffinitive Cu4I4 cluster and one carboxylate group to one COO-affinitive In(III) ion, each bifunctional nia- ligand takes its carboxylate group to link a 6-coordinated In(III) ion in an approximate octahedral surrounding to constitute a 6-connected [In3O(CO2)6] moiety (Fig. 1c, 1d, S1), while it utilizes the remaining N-donor center to join a 4-coordinated Cu(I) center to make up a 4-connected [Cu4I4N4] moiety in a tetrahedral coordination geometry (Fig. 1b) where all the observed In-O, CuI and Cu-N bond lengths are in the range of 2.043(0) - 2.180(0) Å, 2.617(0) - 2.711(0) Å and 2.016(0) Å, respectively. It should be noted here is that there are many disordered charge-balancing NO3- counter anions lying inside the extra-large solvent accessible interspace, which leads to the final charge equilibrium. In this 3-dimensional structure, InOF-8 exhibits 1-dimensional hexagonal channels alternately divided by these [Cu4I4N4] moieties and [In3O(CO2)6] moieties. As depicted in Fig. 2c, the
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interconnection of 6 Cu4I4 clusters and 6 [In3O(CO2)6] building blocks defines the cross section of the nearly hexagonal channel with the approximate size of 18.9 Å by the internal edge of two opposite Cu4I4 clusters and 36.1 Å by the external edge of two opposite [In3O(CO2)6] units along the c-axis, respectively. Carefully observed, we can find that there is a micro-sized cage between two neighbouring [In3O(CO2)6] moieties along the c-axis, which is constituted by 3 Cu4I4 clusters, 2 [In3O(CO2)6] moieties and 6 nia- ligands, with a diameter of 4.8 Å sphere inside (Fig. 2a, S2). Therefore, the overall structure of InOF-8, integrated with two types of metallic clusters in a cluster-by-cluster way through these bridging nia- ligands, is a highly porous MOF structure with the coexistence of microporous cages and 1-dimensional channels (Fig. 2c, S4). Calculated by PLATON program (probe size = 1.2 Å), the total free volume of InOF-8 with the removal of chargebalancing NO3- anions and disordered guest solvent molecules is determined to be ~60.6% (potential solvent area volume = 7124.0 Å3; per unit cell volume = 11760.0 Å3), and the theoretical pore volume is around 0.437 cm3 g-1. Before desolvation and activation process, this single crystal material keeps its intact structure in pure acetonitrile solvent, which is confirmed by the PXRD test (Fig. S5). After solvent-exchange process, the permanent porosity of desolvated material has also been confirmed by the experimental N2 sorption isotherm under liquid nitrogen temperature, which exhibits a reversible type-I N2 isotherm verifying the retention of microporosity with the saturated uptake of 155.3 cm3 g-1 at 77 K (Fig. S8a). Meanwhile, we investigate the volumetric hydrogen sorption capacity at 77 K and 87 K. All the H2 isotherms show rapid kinetics and good reversibility without any hysteresis (Fig. S8c). The H2 uptake capacity is up to 95.2 cm3 g-1 (0.85 wt %) at 77 K and 1.0 bar, and 66.6 cm3 g-1 (0.59 wt %) at 87 K and 1.0 bar. These experimentally obtained values in hydrogen capacity are quite comparable with those well-known microporous MOF materials at the same condition.9,14 Moreover, the adsorption heat
Fig. 2 (a) Micro-sized cages between Cu4I4 clusters and In3O clusters. (b) The dimension of hexagonal channels viewed along the a-axis. (c) 3D tubular structure running along c-axis.
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Fig. 3 (a) CO2, CH4 and N2 adsorption isotherm curves in the range of 0 ~ 110 kPa at 273 K. (b) Adsorption selectivity of CO2 over CH4 or N2.
This journal is © The Royal Society of Chemistry [year]
This work was financially supported by the 973 Program (2013CB933200; 2011CB932504), National Nature Science Foundation of China (21131006), and the CAS/SAFEA International Partnership Program for Creative Research Teams.
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Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China b University of the Chinese Academy of Sciences, Beijing, 100049, China *To whom correspondence should be addressed: Email:[email protected]; Fax: +86-591-83794946; Tel: +86-59183792460 Crystal data for InOF-8: C6H4CuIIn0.50NO2.67, Mr = 380.63, light yellow, 0.12×0.06×0.06 mm3, trigonal, space group P6/mcc (No. = 192), a = b = 21.9173(4) Å, c = 28.2685(4) Å, V = 11760.00(35) Å3, T = 173(2) K, Z = 24, Dc = 1.290 g cm-3, λ = 0.71073 Å, F(000) = 4196, GOF = 1.172, R1 and wR2 are 0.0960 and 0.2851, respectively. CCDC No. 998993. Full experimental details, TGA, PXRD and EA images, and extra gas sorption isotherms are presented in the Supporting Information. 1 (a) Zhou, H. C.; Long, J. R.; Yaghi, O. M. Chem. Rev. 2012, 112, 673. (b) Furukawa, S.; Reboul, J.; Diring, S.; Sumida, K.; Kitagawa, S. Chem. Soc. Rev. 2014, 43, 5700. (c) Serre, C.; Kitagawa, S.; Dietzel, P. D. C. Microporous Mesoporous Mater. 2012, 157, 1. (d) Lin, Z. J.; Lü, J.; Hong, M.; Cao, R. Chem. Soc. Rev. 2014, 43, 5867. 2 (a) Yang, S. H.; Sun, J. L.; Ramirez-Cuesta, A. J.; Callear, S. K.; David, W. I. F.; Anderson, D. P.; Newby, R.; Blake, A. J.; Parker, J. E.; Tang, C. C.; Schroder, M. Nat. Chem. 2012, 4, 887. (b) Zheng, B. S.; Bai, J. F.; Duan, J. G.; Wojtas, L.; Zaworotko, M. J. J. Am. Chem. Soc. 2011, 133, 748. (c) Wu, D.; Maurin, G.; Yang, Q.; Serre, C.; Jobic, H.; Zhong, C. J. Mater. Chem. A. 2014, 2, 1657. (d) Liu, Y.; Chen, Y. P.; Liu, T. F.; Yakovenko, A. A.; Raiff, A. M.; Zhou, H. C. Crystengcomm. 2013, 15, 9688. 3 (a) Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. T.; Kim, J.; O'Keeffe, M.; Yaghi, O. M. Science. 2003, 300, 1127. (b) Lu, W. G.; Yuan, D. Q.; Makal, T. A.; Li, J. R.; Zhou, H. C. Angew. Chem. Int. Ed. 2012, 51, 1580. (c) Li, B. Y.; Zhang, Z. J.; Li, Y.; Yao, K. X.; Zhu, Y. H.; Deng, Z. Y.; Yang, F.; Zhou, X. J.; Li, G. H.; Wu, H. H.; Nijem, N.; Chabal, Y. J.; Lai, Z. P.; Han, Y.; Shi, Z.; Feng, S. H.; Li, J. Angew. Chem. Int. Ed. 2012, 51, 1412. 4 (a) Liu, B.; Tu, M.; Fischer, R. A. Angew. Chem. Int. Ed. 2013, 52, 3402. (b) Xu, H.; Cai, J.; Xiang, S.; Zhang, Z.; Wu, C.; Rao, X.; Cui, Y.; Yang, Y.; Krishna, R.; Chen, B.; Qian, G. J. Mater. Chem. A. 2013, 1, 9916. (c) Chen, K. J.; Lin, R. B.; Liao, P. Q.; He, C. T.; Lin, J. B.; Xue, W.; Zhang, Y. B.; Zhang, J. P.; Chen, X. M. Cryst. Growth Des. 2013, 13, 2118. 5 (a) He, L. C.; Liu, Y.; Liu, J. Z.; Xiong, Y. S.; Zheng, J. Z.; Liu, Y. L.; Tang, Z. Y. Angew. Chem. Int. Ed. 2013, 52, 3741. (b) Zhao, D.; Tan, S. W.; Yuan, D. Q.; Lu, W. G.; Rezenom, Y. H.; Jiang, H. L.; Wang, L. Q.; Zhou, H. C. Adv. Mater. 2011, 23, 90. (c) Yanai, N.; Uemura, T.; Kitagawa, S. Chem. Mater. 2012, 24, 4744. 6 (a) Deria, P.; Mondloch, J. E.; Karagiaridi, O.; Bury, W.; Hupp, J. T.; Farha, O. K. Chem. Soc. Rev. 2014, 43, 5896. (b) McKellar, S. C., Graham, A. J., Allan, D. R., Mohideen, M. I. H., Morris R. E., Moggach, S. A. Nanoscale, 2014, 6, 4163. 7 (a) Lalonde, M.; Bury, W.; Karagiaridi, O.; Brown, Z.; Hupp, J. T.; Farha, O. K. J. Mater. Chem. A. 2013, 1, 5453. (b) Brozek C. K., and Dincă, M. J. Am. Chem. Soc., 2013, 135, 12886. 8 (a) Yu, J. C.; Cui, Y. J.; Wu, C. D.; Yang, Y.; Wang, Z. Y.; O'Keeffe, M.; Chen, B. L.; Qian, G. D. Angew. Chem. Int. Ed. 2012, 51, 10542. (b) Xue, Y. S.; He, Y. B.; Zhou, L.; Chen, F. J.; Xu, Y.; Du, H. B.; You, X. Z.; Chen, B. L. J. Mater. Chem. A. 2013, 1, 4525. (c) Gao, W.-Y.; Zhang, Z.; Cash, L.; Wojtas, L.; Chen, Y.-S.; Ma, S. Crystengcomm. 2013, 15, 9320. (d) Yuan, B. Z.; Ma, D. Y.; Wang, X.; Li, Z.; Li, Y. W.; Liu, H. M.; He, D. H. Chem. Commun. 2012, 48, 1135. (e) Gu, J. M.; Kim, S. J.; Kim, Y.; Huh, S. Crystengcomm. 2012, 14, 1819.
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of hydrogen is simulated by the Clausius-Clapeyron equation and its value at zero coverage for InOF-8 is calculated to be ~6.51 kJ mol-1, and drops gradually and then increases slowly with the incremental H2 loading (Fig. S8d). In this case, we attribute the most of H2 uptake capacity to the intrinsically large guestaccessible volume, especially the extra-large opening channels, while the relatively low binding affinity is due to its possible open metal sites after removing terminally coordinated H2O molecules in [In3O(CO2)6] building blocks or even incomplete activation. The special cage-and-channel-coexisting structure inspires us to further explore the potential applications in carbon dioxide gas storage and separation. The single component low-pressure gas sorption isotherms for InOF-8 toward CO2, CH4 and N2 at 273 K are recorded by utilizing volumetric measurement method and presented in Fig. 3a. At 273 K and 1.0 bar, the total uptake of CO2 is 66.2 cm3 g-1 (2.95 mmol g-1, 129.8 mg g-1), which is much higher than these corresponding values of CH4 and N2 isotherms. At ambient pressure, the uptake values are just 16.6 cm3 g-1 (0.74 mmol g-1, 11.84 mg g-1) and 4.8 cm3 g-1 (0.21 mmol g-1, 5.88 mg g-1) at 273 K for CH4 and N2, respectively. Therefore, the ideal adsorbed solution theory15 has been adopted to investigate the CO2/CH4 and CO2/N2 gas separation16 and the results show us that InOF-8 exhibits a very high selectivity value of 45.2 in a 20:80 molar ratio of CO2 and N2 mixtures at 273 K and 1.0 bar (Fig. 3b). Moreover, at 1.0 bar, the predicted CO2/CH4 selectivity value is 8.3 at 273 K from equimolar gas-phase mixtures. The thermal gravimetric analysis and powder X-ray diffraction show that the desolvated sample retains well its crystallinity after the activation process (Fig. S5, S6).
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Qian, J.; Jiang, F.; Zhang, L.; Su, K.; Pan, J.; Li, Q.; Yuan, D.; Hong, M. Chem. Commun. 2014, 50, 1678. 10 (a) C.Volkringer, T. Loiseau. Mater. Res. Bull. 2006, 41, 948. (b) S. T. Zheng, J. T. Bu, Y. Li, T. Wu, F. Zuo, P. Feng, X. Bu. J. Am. Chem. Soc. 2010, 132, 17062. (b) Meng, X.; Song, X. Z.; Song, S. Y.; Yang, G. C.; Zhu, M.; Hao, Z. M.; Zhao, S. N.; Zhang, H. J.; Chem. Commun., 2013, 49, 8483. (c) Xu, C.; Hedin, N.; Shi, H. T.; Zhang, Q. F.; Chem. Commun., 2014, 50, 3710. (d) Fang, W. H.; Yang, G. Y.; Inorg. Commun., 2014, 53, 5631. 11 (a) Zheng, S. T.; Bu, J. T.; Li, Y. F.; Wu, T.; Zuo, F.; Feng, P. Y.; Bu, X. H. J. Am. Chem. Soc. 2010, 132, 17062. (b) Qian, J.; Jiang, F.; Yuan, D.; Li, X.; Zhang, L.; Su, K.; Hong, M. J. Mater. Chem. A. 2013, 1, 9075. 12 Qian, J. J.; Jiang, F. L.; Yuan, D. Q.; Wu, M. Y.; Zhang, S. Q.; Zhang, L. J.; Hong, M. C. Chem. Commun. 2012, 48, 9696.
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13 (a) Zheng, S. T.; Bu, J. J.; Wu, T.; Chou, C. T.; Feng, P. Y.; Bu, X. H. Angew. Chem. Int. Ed. 2011, 50, 8858. (b) X. J.; Lu, Z. H.; Xu, Q. Chem. Commun. 2010, 46, 7400. (c) Zhao, X.; Bu, X.; TaoWu; Zheng, S.-T.; Wang, L.; Feng, P. Nat. Commun. 2013, 4, 2344. 14 (a) Chui, S. S. Y.; Lo, S. M. F.; Charmant, J. P. H.; Orpen, A. G.; Williams, I. D. Science. 1999, 283, 1148. (b) Yan, Y.; Suyetin, M.; Bichoutskaia, E.; Blake, A. J.; Allan, D. R.; Barnett, S. A.; Schroder, M. Chem. Sci. 2013, 4, 1731. (c) Qian, J. J.; Jiang, F. L.; Su, K. Z.; Pan, J.; Zhang, L. J.; Li, X. J.; Yuan, D. Q.; Hong, M. C. J. Mater. Chem. A. 2013, 1, 10631. 15 A. L. Myers and J. M. Prausnitz, AIChE J. 1965, 11, 121. 16 (a) Rodenas, T.; Dalen, M. v.; García-Pérez, E.; Serra-Crespo, P.; Zornoza, B.; Kapteijn, F. J. G. Adv. Funct. Mater. 2014, 24, 249. (b) Nugent, P. S.; Rhodus, V. L.; Pham, T.; Forrest, K.; Wojtas, L.; Space, B.; Zaworotko, M. J. J. Am. Chem. Soc. 2013, 135, 10950. (c) Kim, J. H.; Abouelnasr, M.; Lin, L. C.; Smit, B. J. Am. Chem. Soc. 2013, 135, 7545.
This journal is © The Royal Society of Chemistry [year]
ChemComm Accepted Manuscript
DOI: 10.1039/C4CC07611G
ChemComm Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. Qian, F. Jiang, K. Su, J. Pan, Z. Xue, L. Liang, P. P. Bag and M. Hong, Chem. Commun., 2014, DOI: 10.1039/C4CC07611G.
This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains.
www.rsc.org/chemcomm
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ChemComm
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DOI: 10.1039/C4CC07611G
Cite this: DOI: 10.1039/c0xx00000x
ARTICLE TYPE
www.rsc.org/xxxxxx
Heterometallic cluster-based indium-organic framework
5
10
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x With the help of the ligand-oriented method, we have successfully embedded independent copper-based units in indium-organic framework system for the first time, in which the Cu4I4 clusters and In3O(CO2)6 clusters coexist. This heterometallic cluster-based framework InOF-8 has a large porosity with extra-open channels along c-axis, and its sorption capacity has been also investigated.
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Among solid state porous materials, such as carbon-based materials, natural zeolites, covalent-organic materials (COFs) and metal-organic frameworks (MOFs), these MOF materials stand out for their well-refined structures and permanent porosity.1 Numerous experimental and theoretical researches have confirmed that MOF materials of high crystallinity turn out to be promising platform for carbon dioxide capture,2 hydrogen storage,3 hydrocarbon separation4 and drug delivery5 in the past decades. Therefore, it is of great importance for MOF chemists to design and synthesize novel multifunctional materials with various organic ligands and inorganic metal units, including single-metal-ion-based clusters and heterometallic clusters. Recently, post-synthetic method6 and transmetalation method,7 routes to obtain isoreticular MOF networks with preserved crystallinity and high surface area and structural features of the original frameworks, have been extensively utilized for the construction of MOF structures. However, these methods might not be always suitable and compatible for the well-studied porous indium-organic frameworks (InOFs). Experimentally speaking, In(III) ions are so COO--affinitive centers with high coordination numbers8 that people are more likely to select multicarboxylate ligands to prepare stable InOF materials, in which most of previously reported InOF crystals are only constructed from the combination of In(III) centers and the carboxylate ligands or functionalized carboxylate ligands, while heterometallic InOF structures or heterometallic cluster-based InOF structures are rarely seen. Very recently, we reported an interesting zinc-based MOF structure (FJI-3) on Chem. Commun., in which it simultaneously incorporated 4-connected Zn2(CO2)4 paddle wheels, topologically equivalent 6-connected Zn3O(CO2)6 trimer and Zn4O(CO2)6 secondary building units (SBUs), featuring a new hexanodal topology.9 In this case, the integration of typical single-metal-ionbased SBUs in one MOF structure has been also confirmed as a facile and ingenious method for synthesizing new InOF This journal is © The Royal Society of Chemistry [year]
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materials.10 Generally speaking, indium(III) ions tend to generate three types of SBU-based coordination frameworks throughout the literatures, namely, 8-coordinated In(CO2)4 monomers,11 infinite In(OH)(CO2)2 chains12 and 6-connected In3O(CO2)6 cluster trimers.13 Therefore, it is still a challenging task to obtain porous heterometallic InOF structures from these In(III)-based SUBs together with other metal building units. Our group has long been seeking to synthesize solid state porous materials particularly based on main group element In(III). Thinking outside the box, we has been innovatively embedded functional Cu(I)-based units in the InOF system for the first time. In our new perspective, by taking the bifunctional ligand-directed method, called Bifunctional Method, it is effective to construct InOF materials where COO--affinitive In(III) ions only bind to carboxylate groups while N-affinitive Cu(I)-based units only bind to pyridyl N-centers based on the bifunctional ligands. And in this work, we report one intriguing heterometallic cluster-based InOF structure: [(In3O)2(Cu4I4)3(nia)12(H2O)6][NO3)2]•Solvent (InOF-8, Hnia = nicotinic acid) based on two kinds of singlemetal-ion-based clusters, which comprises classic In3O(CO2)6 clusters and tetrahedral Cu4I4 clusters. Moreover, sorption behaviour of this desolvated InOF-8 material has been analyzed owing to its open pore environment, and its IAST calculation has also been conducted for their selectivity at low pressure region.
Fig. 1 a) Highlighted asymmetric unit of InOF-8 and the coordination environment of nia- ligand; tetrahedral Cu(I) centers and octahedral In(III) centers. b) 4-coordinated Cu(I)-based [Cu4I4N4] moiety. c) and d) 6coordinated In(III)-based [In3O(CO2)6] moiety.
[journal], [year], [vol], 00–00 | 1
ChemComm Accepted Manuscript
Published on 16 October 2014. Downloaded by Tulane University on 20/10/2014 10:24:06.
Jinjie Qian,a,b Feilong Jiang,a Kongzhao Su,a,b Jie Pan,a,b Zhenzhen Xue,a,b Linfeng Liang,a,b Partha Pratim Bag,a and Maochun Hong*a
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For light yellow stick-like single crystals of InOF-8, they are successfully and solvothermally prepared by heating the mixture of In(NO3)3 salt, cuprous iodide salt and Hnia ligand in a 1:2:4 molar ratio in DMA/MeCN mixed solution (1:1, v/v; DMA = N,N'-diethylformamide; more detail please refer to the Section S1 in the Supporting Information) at 120 oC for one week. The phase purity of the microcrystal product has been confirmed by the powder X-ray diffraction (PXRD) analysis (Fig. S5). Then the resultant framework formula is defined as a positive [(In3O)2(Cu4I4)3(nia)12(H2O)6]2+ network which is calculated from the combination of thermogravimetric analysis (TGA) curve and elemental analysis (EA) data after the SQUEEZE process. It is revealed by single crystal X-ray diffraction analysis that InOF-8 is crystallized in the trigonal space group P6/mmc with cell parameters a = b = 21.9173(4) Å, c = 28.2685(4) Å, V = 11760.0(3) Å3 (refer to Table S1), and its asymmetric unit consists of half a In(III) ion, one quarter of Cu4I4 cluster, one nialigand, one sixth µ3-O2- anion and half a terminally coordinated water molecule as shown in Fig. 1a. In the coordination environment, through the way one pyridyl N atom to one Naffinitive Cu4I4 cluster and one carboxylate group to one COO-affinitive In(III) ion, each bifunctional nia- ligand takes its carboxylate group to link a 6-coordinated In(III) ion in an approximate octahedral surrounding to constitute a 6-connected [In3O(CO2)6] moiety (Fig. 1c, 1d, S1), while it utilizes the remaining N-donor center to join a 4-coordinated Cu(I) center to make up a 4-connected [Cu4I4N4] moiety in a tetrahedral coordination geometry (Fig. 1b) where all the observed In-O, CuI and Cu-N bond lengths are in the range of 2.043(0) - 2.180(0) Å, 2.617(0) - 2.711(0) Å and 2.016(0) Å, respectively. It should be noted here is that there are many disordered charge-balancing NO3- counter anions lying inside the extra-large solvent accessible interspace, which leads to the final charge equilibrium. In this 3-dimensional structure, InOF-8 exhibits 1-dimensional hexagonal channels alternately divided by these [Cu4I4N4] moieties and [In3O(CO2)6] moieties. As depicted in Fig. 2c, the
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interconnection of 6 Cu4I4 clusters and 6 [In3O(CO2)6] building blocks defines the cross section of the nearly hexagonal channel with the approximate size of 18.9 Å by the internal edge of two opposite Cu4I4 clusters and 36.1 Å by the external edge of two opposite [In3O(CO2)6] units along the c-axis, respectively. Carefully observed, we can find that there is a micro-sized cage between two neighbouring [In3O(CO2)6] moieties along the c-axis, which is constituted by 3 Cu4I4 clusters, 2 [In3O(CO2)6] moieties and 6 nia- ligands, with a diameter of 4.8 Å sphere inside (Fig. 2a, S2). Therefore, the overall structure of InOF-8, integrated with two types of metallic clusters in a cluster-by-cluster way through these bridging nia- ligands, is a highly porous MOF structure with the coexistence of microporous cages and 1-dimensional channels (Fig. 2c, S4). Calculated by PLATON program (probe size = 1.2 Å), the total free volume of InOF-8 with the removal of chargebalancing NO3- anions and disordered guest solvent molecules is determined to be ~60.6% (potential solvent area volume = 7124.0 Å3; per unit cell volume = 11760.0 Å3), and the theoretical pore volume is around 0.437 cm3 g-1. Before desolvation and activation process, this single crystal material keeps its intact structure in pure acetonitrile solvent, which is confirmed by the PXRD test (Fig. S5). After solvent-exchange process, the permanent porosity of desolvated material has also been confirmed by the experimental N2 sorption isotherm under liquid nitrogen temperature, which exhibits a reversible type-I N2 isotherm verifying the retention of microporosity with the saturated uptake of 155.3 cm3 g-1 at 77 K (Fig. S8a). Meanwhile, we investigate the volumetric hydrogen sorption capacity at 77 K and 87 K. All the H2 isotherms show rapid kinetics and good reversibility without any hysteresis (Fig. S8c). The H2 uptake capacity is up to 95.2 cm3 g-1 (0.85 wt %) at 77 K and 1.0 bar, and 66.6 cm3 g-1 (0.59 wt %) at 87 K and 1.0 bar. These experimentally obtained values in hydrogen capacity are quite comparable with those well-known microporous MOF materials at the same condition.9,14 Moreover, the adsorption heat
Fig. 2 (a) Micro-sized cages between Cu4I4 clusters and In3O clusters. (b) The dimension of hexagonal channels viewed along the a-axis. (c) 3D tubular structure running along c-axis.
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ChemComm Accepted Manuscript
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Fig. 3 (a) CO2, CH4 and N2 adsorption isotherm curves in the range of 0 ~ 110 kPa at 273 K. (b) Adsorption selectivity of CO2 over CH4 or N2.
This journal is © The Royal Society of Chemistry [year]
This work was financially supported by the 973 Program (2013CB933200; 2011CB932504), National Nature Science Foundation of China (21131006), and the CAS/SAFEA International Partnership Program for Creative Research Teams.
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Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China b University of the Chinese Academy of Sciences, Beijing, 100049, China *To whom correspondence should be addressed: Email:[email protected]; Fax: +86-591-83794946; Tel: +86-59183792460 Crystal data for InOF-8: C6H4CuIIn0.50NO2.67, Mr = 380.63, light yellow, 0.12×0.06×0.06 mm3, trigonal, space group P6/mcc (No. = 192), a = b = 21.9173(4) Å, c = 28.2685(4) Å, V = 11760.00(35) Å3, T = 173(2) K, Z = 24, Dc = 1.290 g cm-3, λ = 0.71073 Å, F(000) = 4196, GOF = 1.172, R1 and wR2 are 0.0960 and 0.2851, respectively. CCDC No. 998993. Full experimental details, TGA, PXRD and EA images, and extra gas sorption isotherms are presented in the Supporting Information. 1 (a) Zhou, H. C.; Long, J. R.; Yaghi, O. M. Chem. Rev. 2012, 112, 673. (b) Furukawa, S.; Reboul, J.; Diring, S.; Sumida, K.; Kitagawa, S. Chem. Soc. Rev. 2014, 43, 5700. (c) Serre, C.; Kitagawa, S.; Dietzel, P. D. C. Microporous Mesoporous Mater. 2012, 157, 1. (d) Lin, Z. J.; Lü, J.; Hong, M.; Cao, R. Chem. Soc. Rev. 2014, 43, 5867. 2 (a) Yang, S. H.; Sun, J. L.; Ramirez-Cuesta, A. J.; Callear, S. K.; David, W. I. F.; Anderson, D. P.; Newby, R.; Blake, A. J.; Parker, J. E.; Tang, C. C.; Schroder, M. Nat. Chem. 2012, 4, 887. (b) Zheng, B. S.; Bai, J. F.; Duan, J. G.; Wojtas, L.; Zaworotko, M. J. J. Am. Chem. Soc. 2011, 133, 748. (c) Wu, D.; Maurin, G.; Yang, Q.; Serre, C.; Jobic, H.; Zhong, C. J. Mater. Chem. A. 2014, 2, 1657. (d) Liu, Y.; Chen, Y. P.; Liu, T. F.; Yakovenko, A. A.; Raiff, A. M.; Zhou, H. C. Crystengcomm. 2013, 15, 9688. 3 (a) Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. T.; Kim, J.; O'Keeffe, M.; Yaghi, O. M. Science. 2003, 300, 1127. (b) Lu, W. G.; Yuan, D. Q.; Makal, T. A.; Li, J. R.; Zhou, H. C. Angew. Chem. Int. Ed. 2012, 51, 1580. (c) Li, B. Y.; Zhang, Z. J.; Li, Y.; Yao, K. X.; Zhu, Y. H.; Deng, Z. Y.; Yang, F.; Zhou, X. J.; Li, G. H.; Wu, H. H.; Nijem, N.; Chabal, Y. J.; Lai, Z. P.; Han, Y.; Shi, Z.; Feng, S. H.; Li, J. Angew. Chem. Int. Ed. 2012, 51, 1412. 4 (a) Liu, B.; Tu, M.; Fischer, R. A. Angew. Chem. Int. Ed. 2013, 52, 3402. (b) Xu, H.; Cai, J.; Xiang, S.; Zhang, Z.; Wu, C.; Rao, X.; Cui, Y.; Yang, Y.; Krishna, R.; Chen, B.; Qian, G. J. Mater. Chem. A. 2013, 1, 9916. (c) Chen, K. J.; Lin, R. B.; Liao, P. Q.; He, C. T.; Lin, J. B.; Xue, W.; Zhang, Y. B.; Zhang, J. P.; Chen, X. M. Cryst. Growth Des. 2013, 13, 2118. 5 (a) He, L. C.; Liu, Y.; Liu, J. Z.; Xiong, Y. S.; Zheng, J. Z.; Liu, Y. L.; Tang, Z. Y. Angew. Chem. Int. Ed. 2013, 52, 3741. (b) Zhao, D.; Tan, S. W.; Yuan, D. Q.; Lu, W. G.; Rezenom, Y. H.; Jiang, H. L.; Wang, L. Q.; Zhou, H. C. Adv. Mater. 2011, 23, 90. (c) Yanai, N.; Uemura, T.; Kitagawa, S. Chem. Mater. 2012, 24, 4744. 6 (a) Deria, P.; Mondloch, J. E.; Karagiaridi, O.; Bury, W.; Hupp, J. T.; Farha, O. K. Chem. Soc. Rev. 2014, 43, 5896. (b) McKellar, S. C., Graham, A. J., Allan, D. R., Mohideen, M. I. H., Morris R. E., Moggach, S. A. Nanoscale, 2014, 6, 4163. 7 (a) Lalonde, M.; Bury, W.; Karagiaridi, O.; Brown, Z.; Hupp, J. T.; Farha, O. K. J. Mater. Chem. A. 2013, 1, 5453. (b) Brozek C. K., and Dincă, M. J. Am. Chem. Soc., 2013, 135, 12886. 8 (a) Yu, J. C.; Cui, Y. J.; Wu, C. D.; Yang, Y.; Wang, Z. Y.; O'Keeffe, M.; Chen, B. L.; Qian, G. D. Angew. Chem. Int. Ed. 2012, 51, 10542. (b) Xue, Y. S.; He, Y. B.; Zhou, L.; Chen, F. J.; Xu, Y.; Du, H. B.; You, X. Z.; Chen, B. L. J. Mater. Chem. A. 2013, 1, 4525. (c) Gao, W.-Y.; Zhang, Z.; Cash, L.; Wojtas, L.; Chen, Y.-S.; Ma, S. Crystengcomm. 2013, 15, 9320. (d) Yuan, B. Z.; Ma, D. Y.; Wang, X.; Li, Z.; Li, Y. W.; Liu, H. M.; He, D. H. Chem. Commun. 2012, 48, 1135. (e) Gu, J. M.; Kim, S. J.; Kim, Y.; Huh, S. Crystengcomm. 2012, 14, 1819.
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of hydrogen is simulated by the Clausius-Clapeyron equation and its value at zero coverage for InOF-8 is calculated to be ~6.51 kJ mol-1, and drops gradually and then increases slowly with the incremental H2 loading (Fig. S8d). In this case, we attribute the most of H2 uptake capacity to the intrinsically large guestaccessible volume, especially the extra-large opening channels, while the relatively low binding affinity is due to its possible open metal sites after removing terminally coordinated H2O molecules in [In3O(CO2)6] building blocks or even incomplete activation. The special cage-and-channel-coexisting structure inspires us to further explore the potential applications in carbon dioxide gas storage and separation. The single component low-pressure gas sorption isotherms for InOF-8 toward CO2, CH4 and N2 at 273 K are recorded by utilizing volumetric measurement method and presented in Fig. 3a. At 273 K and 1.0 bar, the total uptake of CO2 is 66.2 cm3 g-1 (2.95 mmol g-1, 129.8 mg g-1), which is much higher than these corresponding values of CH4 and N2 isotherms. At ambient pressure, the uptake values are just 16.6 cm3 g-1 (0.74 mmol g-1, 11.84 mg g-1) and 4.8 cm3 g-1 (0.21 mmol g-1, 5.88 mg g-1) at 273 K for CH4 and N2, respectively. Therefore, the ideal adsorbed solution theory15 has been adopted to investigate the CO2/CH4 and CO2/N2 gas separation16 and the results show us that InOF-8 exhibits a very high selectivity value of 45.2 in a 20:80 molar ratio of CO2 and N2 mixtures at 273 K and 1.0 bar (Fig. 3b). Moreover, at 1.0 bar, the predicted CO2/CH4 selectivity value is 8.3 at 273 K from equimolar gas-phase mixtures. The thermal gravimetric analysis and powder X-ray diffraction show that the desolvated sample retains well its crystallinity after the activation process (Fig. S5, S6).
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13 (a) Zheng, S. T.; Bu, J. J.; Wu, T.; Chou, C. T.; Feng, P. Y.; Bu, X. H. Angew. Chem. Int. Ed. 2011, 50, 8858. (b) X. J.; Lu, Z. H.; Xu, Q. Chem. Commun. 2010, 46, 7400. (c) Zhao, X.; Bu, X.; TaoWu; Zheng, S.-T.; Wang, L.; Feng, P. Nat. Commun. 2013, 4, 2344. 14 (a) Chui, S. S. Y.; Lo, S. M. F.; Charmant, J. P. H.; Orpen, A. G.; Williams, I. D. Science. 1999, 283, 1148. (b) Yan, Y.; Suyetin, M.; Bichoutskaia, E.; Blake, A. J.; Allan, D. R.; Barnett, S. A.; Schroder, M. Chem. Sci. 2013, 4, 1731. (c) Qian, J. J.; Jiang, F. L.; Su, K. Z.; Pan, J.; Zhang, L. J.; Li, X. J.; Yuan, D. Q.; Hong, M. C. J. Mater. Chem. A. 2013, 1, 10631. 15 A. L. Myers and J. M. Prausnitz, AIChE J. 1965, 11, 121. 16 (a) Rodenas, T.; Dalen, M. v.; García-Pérez, E.; Serra-Crespo, P.; Zornoza, B.; Kapteijn, F. J. G. Adv. Funct. Mater. 2014, 24, 249. (b) Nugent, P. S.; Rhodus, V. L.; Pham, T.; Forrest, K.; Wojtas, L.; Space, B.; Zaworotko, M. J. J. Am. Chem. Soc. 2013, 135, 10950. (c) Kim, J. H.; Abouelnasr, M.; Lin, L. C.; Smit, B. J. Am. Chem. Soc. 2013, 135, 7545.
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ChemComm Accepted Manuscript
DOI: 10.1039/C4CC07611G
