Synthesis of Homochiral Zeolitic Tetrazolate Frameworks Based on

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Synthesis of Homochiral Zeolitic Tetrazolate Frameworks based on Enantiopure Porphyrin-like subunits Juan Liu, Fei Wang, and Jian Zhang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00877 • Publication Date (Web): 22 Aug 2017 Downloaded from http://pubs.acs.org on August 23, 2017

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Crystal Growth & Design

Synthesis of Homochiral Zeolitic Tetrazolate Frameworks based on Enantiopure Porphyrin-like subunits Juan Liu,†,‡ Fei Wang,*,† and Jian Zhang*,† †

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of

Matter, Chinese Academy of Sciences, Fuzhou, Fujian, P. R. China 350002. ‡

University of Chinese Academy of Sciences, 100049 Beijing, P. R. China

KEYWORDS: Enantiopure tetrazole ligands, Homochiral Zeolitic Tetrazolate Frameworks, Enantiopure Porphyrin-like subunits.

ABSTRACT: The assembly of enantiopure tetrazoles with cupric ion gives rise to five homochiral zeolitic tetrazolate frameworks （HZTFs）with rich topological nets, in which the similar enantiopure porphyrin-like Cu(5-eatz)2 subunits (SBUs) are captured in-situ and play different roles.

■ INTRODUCTION Homochiral metal−organic frameworks (HMOFs) have attracted great interest due to their promising application in heterogeneous asymmetric catalysis1-5, enantioselective separation6-8 and fluorescence sensing9,10. Among numerous HMOFs with diverse structural features, homochiral zeolitic MOFs (HZMOFs) with 4-connected zeotype topologies continue to attract increasing attention due to their high stability. Currently, although fruits of HMOFs have been reported, the development of HZMOFs is still in its early stage11-13.

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Tremendous eﬀorts have proved that the self-assembly of enantiopure organic ligands with metal ions is the most promising route to construct HMOFs14-18. Recently, some HZMOFs have been successfully synthesized from enantiopure imidazole ligands by our research group19. Our works also prove that tetrazoles with different substituents can be used to construct ZMOFs20. In our previous work, we found the coordination of enantiopure tetrazoles with Cu ions are predictable21,22. For example, (1S)-1-(5-tetrazolyl) ethylamine (5-eatz) is easy to assemble with Cu ions into Cu(5-eatz)2 SBU, which possesses the cis- and trans- configurations as shown in Scheme 1. Such Cu(5-eatz)2 SBUs can act as liner and 4-connected nodes under different conditions. Keeping this in mind, it would be a feasible access to build HZMOFs via utilizing these enantiopure Cu(5-eatz)2 SBUs as the building units.

Schem 1. a) The cis Cu(5-eatz)2 subunit, b) The trans Cu(5-eatz)2 subunit. Based on this consideration, by using the enantiopure tetrazole ligands, (1S)-1-(5tetrazolyl)ethylamine (5-eatz) or (1S)-1-(5-tetrazolyl)isobutylamine (5-iatz) to assemble with copper salts, we successfully synthesize five HZTFs, CuI2CuII(5-eatz)2(CN-)(I-) (1), CuI2CuII(5eatz)2(CN-)(Cl-) (2), [CuI2CuII(5-eatz)2(CN-)2(H2O)].H2O (3), [CuI2CuII(5-eatz)2(CN)2(H2O)2].2H2O (4) and CuICuII (5-iatz)2(I-) (5). In these compounds, the Cu(tetrazolate)2 SBU with cis- or trans-configuration can be obtained under different conditions. Then by adjusting the


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anions as auxiliary ligands, we can tune the final frameworks with different topological nets. These results show that it is an effective way to synthesize new HZMOFs. ■ STRUCTURE DESCRIPTIONS Orange crystals of 1 (and 2) were obtained by hydrothermal reaction of 5-eatz, Na4[Fe(CN)6], CuI (CuCl for 2), and KI (KCl for 2) at 100 °C. Compounds 1 and 2 present the isostructural frameworks with different terminal ligands (I- for 1and Cl-for 2). Both of them crystallize in the monoclinic crystal system with the C2 space group. Therefore, only compound 1 will be discussed in detail. The asymmetric unit of 1 contains three independent Cu ions (Figure 1a). Cu2 is coordinated by two 5-eatz ligands to form a Cu(5-eatz)2 SBU in trans-configuration. Meanwhile, the Cu3 and Cu1 are tetrahedrally coordinated by two N atoms from two 5-eatz, one CN- dissociated from Na4[Fe(CN)6], and one µ2-I- anion. The Cu1 and Cu3 are linked by µ2-Ianion to form the Cu2I SBU. Then each Cu2I SBU is linked by two Cu(5-eatz)2 SBUs and two CN- to generate a 3D framework (Figure 1c). So the Cu2I can be considered as the 4-connected node, the Cu(5-eatz)2 SBU and CN- can be treated as the linkers (Figure 1b). In this way the whole framework can be simplified as the 3-fold interpenetrated dia net (Figure 1d)23,24,25.


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Figure 1. a) The coordinate environment of compound 1 and 2, b) the dia cage, c) the 3D framework of compound 1, d) The 3-fold interpenetration dia topology in 1. In comparison, dark blue crystals of 3 were obtained by using Cu(NO3)2 as copper salts under similar condition. Compound 3 also crystallizes in the monoclinic crystal system with the C2 space group, but the asymmetric unit of 3 just contains two independent Cu ions (Figure 2a). The similar Cu(5-eatz)2 SBU in trans-configuration is observed. The slight difference is that the center Cu1 atom is six coordinated, and two axial positions are occupied by two water molecules. The Cu2 is tetrahedrally coordinated by two N atoms from two 5-eatz ligands and two CN-. Similarly, in compound 1, the Cu(5-eatz)2 SBU also coordinate to four Cu atoms, however, it’s more reasonable to be a planar 4-connected node because of the absence of the µ2-Ianion (Figure 2b). The CN- acts as the linker and the tetrahedral Cu2 acts as tetrahedral 4connected node. So compound 3 has a 4-connected mog-type 3D framework (figure 2b and 2d).


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Figure 2. a) The coordinate environment of compound 3, b) The mog cage of compound 3, c) The 3D framework of compound 3, d) The mog topology of compound 3. Purple crystals of 4 based on cis-Cu(5-eatz)2 SBU were synthesized under similar condition of 3 in absence of ethanol. Compound 4 crystallizes in hexagonal crystal system with space groups of P3121 and it includes three independent Cu ions in the asymmetric unit. The Cu3 atom is coordinated by two 5-eatz ligands to form the cis-Cu(5-eatz)2 SBU. And the Cu3 atom shows almost same coordination mode as that in compound 3. Interestingly, the cis-Cu(5-eatz)2 SBU is chelated to another Cu2 atom by using the two N atoms from two 5-eatz ligands, giving a new Cu2(5-eatz)2 SBU. Each Cu2(5-eatz)2 SBU is coordinated to four Cu1 atoms as the distorted tetrahedral node (Figure 3b). And the Cu1 is also as the tetrahedral node because it is linked by two CN- and two Cu2(5-eatz)2 SBUs. Thus, compound 4 exhibits 4-connected qtz-type framework (Figure 3d).


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Figure 3. The coordinate environment of compound 4, b) two kind tetrahedral nodes of Cu ion and Cu2(5-eatz)2 structure in compound 4, c) The 3D framework of compound 4, d) The qtz topology of compound 4. By employing 5-iatz as the ligand, orange crystals of 5 were achieved and it crystallizes in the orthorhombic P212121 space group. There are two independent Cu ions in the asymmetric unit of 5 (Figure 4a). The Cu1 atom is coordinated by two 5-iatz ligands to form the cis-Cu(5-eatz)2 SBU. Then the cis-Cu(5-iatz)2 SBU is chelated to another Cu2 atom to generate the Cu2(5-iatz)2 SBU. Differently, I- anion is pendent on Cu2 atom as the terminal ligand, and Cu1 adopts square pyramidal coordination geometry, which is coordinated by one N atom from a 5-iatz ligand on the axial position. So the new Cu2(5-iatz)2I SBU is formed and it can also be treated as the


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distorted tetrahedral node (Figure 4b). Lack of the CN-, the Cu2(5-iatz)2I SBU crosslinks each other to form the 3D framework with dia topology (Figure 4c and 4d).

Figure 4. a) The coordinate environment of compound 5, b) The tetrahedral Cu2(5-eatz)2 structure of compound 5, c) The 3D framework of compound 5, d) The dia topology of compound 5. ■ STRUCTURE COMPATRSION To better understand such interesting HZMOFs, we will discuss them together. All of the compounds are mixed valence framework, which can be proved by the XPS characterization (Figure S4). There are four different nets found in these compounds in total. The 3-fold interpenetrated dia net in 1 is composed of Cu2I tetrahedral node, and two different linkers, trans-Cu(5-eatz)2 SBU and CN-. While in 3, trans-Cu(5-eatz)2 SBU acts as the planar 4connected node, and single Cu atom acts as the tetrahedral node, so it has the mog net.


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Differently, cis-Cu(5-eatz)2 SBU is found in 4, which further coordinates to one Cu atom to form a new Cu2(5-eatz)2 SBU as distorted tetrahedral node. Such difference results in the final net from mog to qtz. Compared to 4, Cu2(5-iatz)2I SBU is formed in 5 because the terminal I- anion replaces the µ2-CN-. Just one kind of distorted tetrahedral node with large constituents forms the dia net without interpenetration. For these compounds, we can steadily synthesize the similar components Cu(tetrazolate)2 SBU with cis- or trans-configuration under different conditions. Then by adjusting the anions as auxiliary ligands, we can further tune the exact components of the SBUs and the linkage between different nodes, making the final frameworks with various topological nets. These results demonstrate that this stagey is very effective in the construction of novel HZMOFs.

Figure 5. The assembly of zeolitic chiral tetrazolate frameworks from Cu(5-eatz)2 or Cu2(5eatz)2 subunits.


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■ CONCLUSION In conclusion, the enantiopure porphyrin-like Cu(tetrazolate)2 SBUs can be widely used to construct new HZMOFs with various nets. This work proves that it’s an effective method to construct HZMOFs for future applications.

■ ASSOCIATED CONTENT

Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd. x0xx00000x. Synthetic procedures, IR, PXRD, TG, and single-crystal XRD data (PDF). Accession Codes CCDC 1538789-1538793 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 [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

■AUTHOR INFORMATION Corresponding Author * E-mail: [email protected], [email protected]. Notes


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The authors declare no competing ﬁnancial interest. ■ ACKNOWLEDGMENT This work is supported by NSFC (21573236, 21425102) and Chunmiao Project of Haixi Institute of Chinese Academy of Sciences (CMZX-2015-001). ■ REFERENCES (1) Seo, J. S.; Whang, D.; Lee, H.; Jun, S. I.; Oh, J.; Jeon Y. J.; Kim, K. Nature, 2000, 404, 982– 986. (2) Cho, S. H.; Ma, B.; Nguyen, S. B. T.; Hupp, J. T.; Albrecht-Schmitt, T. E. Chem. Comm. 2006, 24, 2563–2565. (3) Wu, C. D.; Lin, W. Angew. Chem. Int. Ed. 2007, 46, 1075–1078. (4) Wu, P.; He, C.; Wang, J.; Peng, X.; Li, X.; An, Y.; Duan, C. J. Am. Chem. Soc., 2012, 134, 14991−14999. (5) Zhu, C.; Xia, Q.; Chen, X.; Liu, Y.; Du, X.; Cui, Y. ACS Catal. 2016, 6, 7590–7596. (6) Peng, Y.; Gong, T.; Zhang, K.; Lin, X.; Liu, Y.; Jiang, J.; Cui, Y. Nat. Comm. 2014, 5, 4406– 4414. (7) Zhang, S.–Y.; Wojtas, L.; Zaworotko, M. J. J. Am. Chem. Soc., 2015, 137, 12045–12049. (8) Wu, H.–H.; Thibault, C. G.; Wang, H.; Cychosz, K. A.; Thommes, M.; Li, J. Microporous Mesoporous Mater., 2016, 219, 186-189. (9) Wanderley, M. M.; Wang, C.; Wu, C. D.; Lin, W. J. Am. Chem. Soc., 2012, 134, 9050−9053. (10) Rudd, N. D.; Wang, H.; Fuentes-Fernandez, E. M. A.; Teat, S. J.; Chen, F.; Hall, G.; Chabal, Y. J.; Li, J.; ACS Appl. Mater. Interfaces, 2016, 8, 30294–30303. (11) Xu, Z.–X.; Ma, Y.–L.; Zhang, J. Chem. Commun., 2016, 52, 1923–1925.


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For Table of Contents Use Only Synthesis of Homochiral Zeolitic Tetrazolate Frameworks based on Enantiopure Porphyrin-like subunits Juan Liu,†,‡ Fei Wang,*,† and Jian Zhang*,† †State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, P. R. China 350002. ‡University of Chinese Academy of Sciences, 100049 Beijing, P. R. China

The assembly of enantiopure tetrazole with cupric ion gives rise to five homochiral zeolitic frameworks with rich topological nets, in which the similar enantiopure porphyrin-like Cu(5eatz)2 subunits (SBUs) are captured in-situ and play different roles.


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Synthesis of Homochiral Zeolitic Tetrazolate Frameworks Based on

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