The application of polyoxometalate (POM) as building blocks to construct chiral POM-based functionalized frameworks remains a long-standing challenge. In this study, we report a chiral assembly by blending inorganic POMs and organic cyclodextrin (α-CD) molecules on the basis of coordination interactions. {SiW12} anions connect with Mn ions (Mn2+) antiparallel to form a unique all-inorganic layer with significant voids. The similar α-CD layered structure fills the voids of the POM–Mn layers, which are interwoven to form an organic–inorganic hybrid, which is extended by Na+ ions to produce a three-dimensional framework. The stability, chiral separation, chiral catalysis, and proton conductivity of this composite framework are explored.
Rhule, J. T.; Hill, C. L.; Judd, D. A.; Schinazi, R. F. Polyoxometalates in medicine. Chem. Rev. 1998, 98, 327–358.
Wang, M. Y.; Yuan, Y. Y.; Qi, Z. Q.; Chen, J. Y.; Jiang, Z. G.; Zhan, C. H. Two Pseudo- T polyoxometalate-organic cages with the Td-Keggin template. Chem. Mater. 2022, 34, 10501–10508.
Rüther, T.; Hultgren, V. M.; Timko, B. P.; Bond, A. M.; Jackson, W. R.; Wedd, A. G. Electrochemical investigation of photooxidation processes promoted by sulfo-polyoxometalates: Coupling of photochemical and electrochemical processes into an effective catalytic cycle. J. Am. Chem. Soc. 2003, 125, 10133–10143.
Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi, E.; Yazaydin, A. Ö.; Snurr, R. Q.; O'Keeffe, M.; Kim, J. et al. Ultrahigh porosity in metal-organic frameworks. Science 2010, 329, 424–428.
Cheng, D. M.; Gao, Z. X.; Wang, W. W.; Li, S. Q.; Li, B.; Zang, H. Y. Zwitterion-dissociated polyoxometalate electrolytes for solid-state supercapacitors. Polyoxometalates 2023, 2, 9140019.
An, Y.; Wang, L. L.; Jiang, W. Y.; Lv, X. L.; Yuan, G. Q.; Hang, X. X.; Pang, H. Metal-organic framework-based materials for photocatalytic overall water splitting: Status and prospects. Polyoxometalates 2023, 2, 9140030.
Ding, J. H.; Liu, Y. F.; Tian, Z. T.; Lin, P. J.; Yang, F.; Li, K.; Yang, G. P.; Wei, Y. G. Uranyl-silicotungstate-containing hybrid building units {α-SiW9} and {γ-SiW10} with excellent catalytic activities in the three-component synthesis of dihydropyrimidin-2(1 H)-ones. Inorg. Chem. Front. 2023, 10, 3195–3201.
Ren, X. Y.; Chen, B. K.; Zhang, G.; Bi, Y. F.; Dai, L. L.; Yang, G. P. Making one VIV substitution for Mo on classical [MoV2O4]2+ group: The first heterobimetallic Mo-V subunit in polyoxomolybdate-bisphosphonate family. Inorg. Chem. Front. 2023, 10, 5782–5788.
Wang, Y. X.; Lu, Y.; Zhang, W. S.; Dang, T. Y.; Yang, Y. L.; Bai, X.; Liu, S. X. Construction of hydrogel composites with superior proton conduction and flexibility using a new POM-based inorganic-organic hybrid. Polyoxometalates 2022, 1, 9140005.
Wei, Y. G. Polyoxometalates: An interdisciplinary journal focused on all aspects of polyoxometalates. Polyoxometalates 2022, 1, 9140014.
Zang, D. J.; Wang, H. Q. Polyoxometalate-based nanostructures for electrocatalytic and photocatalytic CO2 reduction. Polyoxometalates 2022, 1, 9140006.
Zhang, S. S.; Liu, R. J.; Streb, C.; Zhang, G. J. Design and synthesis of novel polyoxometalate-based binary and ternary nanohybrids for energy conversion and storage. Polyoxometalates 2023, 2, 9140037.
Li, J.; Zhang, D.; Chi, Y. N.; Hu, C. W. Catalytic application of polyoxovanadates in the selective oxidation of organic molecules. Polyoxometalates 2022, 1, 9140012.
Shen, Q. B.; Chen, J. L.; Jing, X.; Duan, C. Y. Polyoxometalate-embedded metal-organic framework as an efficient copper-based monooxygenase for C(sp3)-H bond oxidation via multiphoton excitation. ACS Catal. 2023, 13, 9969–9978.
Xue, R.; Guo, H.; Yang, W.; Huang, S. L.; Yang, G. Y. Cooperation between covalent organic frameworks (COFs) and metal organic frameworks (MOFs): Application of COFs-MOFs hybrids. Adv. Compos. Hybrid. Mater. 2022, 5, 1595–1611.
Zeng, H. M.; Jiang, Z. G.; Zhang, H. W.; Mao, W. T.; Gao, X. H.; Zhan, C. H. An extraordinary OER electrocatalyst based on the Co-Mo synergistic 2D pure inorganic porous framework. Eur. J. Inorg. Chem. 2021, 2021, 2606–2610.
Chen, W. Z.; Yi, X. F.; Zhang, J.; Zhang, L. Heterometallic Mo-Ti Oxo clusters with metal-metal bonds: Preparation and visible-light absorption behaviors. Polyoxometalates 2023, 2, 9140013.
Guan, Y.; Xiao, H. P.; Li, X. X.; Zheng, S. T. Recent advances on the synthesis, structure, and properties of polyoxotantalates. Polyoxometalates 2023, 2, 9140023.
Li, S. R.; Liu, W. D.; Long, L. S.; Zheng, L. S.; Kong, X. J. Recent advances in polyoxometalate-based lanthanide-oxo clusters. Polyoxometalates 2023, 2, 9140022.
Shi, J. Y.; Kumar Gupta, R.; Deng, Y. K.; Sun, D.; Wang, Z. Recent advances in the asymmetrical templation effect of polyoxometalate in silver clusters. Polyoxometalates 2022, 1, 9140010.
Zhang, Y.; Liu, J.; Li, S. L.; Su, Z. M.; Lan, Y. Q. Polyoxometalate-based materials for sustainable and clean energy conversion and storage. EnergyChem 2019, 1, 100021.
Inman, C.; Knaust, J. M.; Keller, S. W. A polyoxometallate-templated coordination polymer: Synthesis and crystal structure of [Cu3(4,4'-bipy)5(MECN)2]PW12O40·2C6H5CN. Chem. Commun. 2002, 156–157.
Vila-Nadàl, L.; Cronin, L. Design and synthesis of polyoxometalate-framework materials from cluster precursors. Nat. Rev. Mater. 2017, 2, 17054.
Liu, J. X.; Zhang, X. B.; Li, Y. L.; Huang, S. L.; Yang, G. Y. Polyoxometalate functionalized architectures. Coord. Chem. Rev. 2020, 414, 213260.
Wang, Y.; Zeng, H. M.; Mao, W. T.; Wang, X. J.; Jiang, Z. G.; Zhan, C. H.; Feng, Y. L. The synthesis and photoluminescence of three porous metal-organic frameworks. Inorg. Chem. Commun. 2021, 129, 108613.
Huang, J. J.; Jiao, L.; Xu, W. Q.; Wang, H. J.; Sha, M.; Wu, Z. C.; Gu, W. L.; Hu, L. Y.; Zhu, C. Z. Amorphous metal-organic frameworks on PtCu hydrogels: Enzyme immobilization platform with boosted activity and stability for sensitive biosensing. J. Hazard. Mater. 2022, 432, 128707.
Hu, M.; Wang, Y.; Yang, J. F.; Sun, Y. N.; Xing, G. X.; Deng, R. G.; Hu, X. F.; Zhang, G. P. Competitive electrochemical immunosensor for maduramicin detection by multiple signal amplification strategy via hemin@Fe-MIL-88NH2/AuPt. Biosens. Bioelectron. 2019, 142, 111554.
Sun, Y.; Jiang, X.; Jin, H.; Gui, R. Ketjen black/ferrocene dual-Doped MOFs and aptamer-coupling gold nanoparticles used as a novel ratiometric electrochemical aptasensor for vanillin detection. Anal. Chim. Acta. 2019, 1083, 101–109.
Cook, T. R.; Zheng, Y. R.; Stang, P. J. Metal-organic frameworks and self-assembled supramolecular coordination complexes: Comparing and contrasting the design, synthesis, and functionality of metal-organic materials. Chem. Rev. 2013, 113, 734–777.
Lee, J. Y.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. B. T.; Hupp, J. T. Metal-organic framework materials as catalysts. Chem. Soc. Rev. 2009, 38, 1450–1459.
Deng, H. X.; Doonan, C. J.; Furukawa, H.; Ferreira, R. B.; Towne, J.; Knobler, C. B.; Wang, B.; Yaghi, O. M. Multiple functional groups of varying ratios in metal-organic frameworks. Science 2010, 327, 846–850.
Luo, G. G.; Pan, Z. H.; Han, B. L.; Dong, G. L.; Deng, C. L.; Azam, M.; Tao, Y. W.; He, J.; Sun, C. F.; Sun, D. Total structure, electronic structure and catalytic hydrogenation activity of metal-deficient chiral polyhydride Cu57 nanoclusters. Angew. Chem., Int. Ed. 2023, 62, e202306849.
Jia, T.; Guan, Z. J.; Zhang, C. K.; Zhu, X. Z.; Chen, Y. X.; Zhang, Q.; Yang, Y.; Sun, D. Eight-electron superatomic Cu31 nanocluster with chiral kernel and Nir-II emission. J. Am. Chem. Soc. 2023, 145, 10355–10363.
Yan, L. K.; López, X.; Carbó, J. J.; Sniatynsky, R.; Duncan, D. C.; Poblet, J. M. On the origin of alternating bond distortions and the emergence of chirality in polyoxometalate anions. J. Am. Chem. Soc. 2008, 130, 8223–8233.
Kortz, U.; Matta, S. Novel, Trimeric Mn-substituted undecatungstosilicate, [(β2-SiW11MnO38OH)3]15−. Inorg. Chem. 2001, 40, 815–817.
Leclerc-Laronze, N.; Marrot, J.; Hervé, G.; Thouvenot, R.; Cadot, E. The heteropolytungstate core {BW13O46}11− derived as monomer, dimer, and trimer. Chemistry 2007, 13, 7234–7245.
Jiang, Z. G.; Wu, X.; Xu, Z. X.; Zhan, C. H.; Zhang, J. Synthesis and photocatalytic activities of two homochiral metal-organic frameworks with cages and hydrogen bonding helices. CrystEngComm 2020, 22, 4206–4209.
Xiao, F. P.; Hao, J.; Zhang, J.; Lv, C. L.; Yin, P. C.; Wang, L. S.; Wei, Y. G. Polyoxometalatocyclophanes: Controlled assembly of polyoxometalate-based chiral metallamacrocycles from achiral building blocks. J. Am. Chem. Soc. 2010, 132, 5956–5957.
Qi, Z. Q.; Wang, M. Y.; Shen, J. C.; Lan, Y. Z.; Jiang, Z. G.; Zhan, C. H. Supramolecular hybrids of chiral waugh polyoxometalate with cyclodextrins. Chem. Commun. 2022, 58, 13616–13619.
Jiang, Z. G.; Mao, W. T.; Huang, D. P.; Wang, Y.; Wang, X. J.; Zhan, C. H. A nonconventional host-guest cubic assembly based on γ-cyclodextrin and a Keggin-type polyoxometalate. Nanoscale 2020, 12, 10166–10171.
Patel, H. A.; Islamoglu, T.; Liu, Z. C.; Nalluri,S. K. M.; Samanta, A.; Anamimoghadam, O.; Malliakas, C. D.; Farha, O. K.; Stoddart, J. F. Noninvasive substitution of K+ sites in cyclodextrin metal-organic frameworks by Li+ ions. J. Am. Chem. Soc. 2017, 139, 11020–11023.
Roy, I.; Stoddart, J. F. Cyclodextrin metal-organic frameworks and their applications. Acc. Chem. Res. 2021, 54, 1440–1453.
Forgan, R. S.; Smaldone, R. A.; Gassensmith, J. J.; Furukawa, H.; Cordes, D. B.; Li, Q. W.; Wilmer, C. E.; Botros, Y. Y.; Snurr, R. Q.; Slawin, A. M. Z. et al. Nanoporous carbohydrate metal-organic frameworks. J. Am. Chem. Soc. 2012, 134, 406–417.
Moussawi, M. A.; Leclerc-Laronze, N.; Floquet, S.; Abramov, P. A.; Sokolov, M. N.; Cordier, S.; Ponchel, A.; Monflier, E.; Bricout, H.; Landy, D. et al. Polyoxometalate, cationic cluster, and γ-cyclodextrin: From primary interactions to supramolecular hybrid materials. J. Am. Chem. Soc. 2017, 139, 12793–12803.
Yang, P.; Zhao, W. L.; Shkurenko, A.; Belmabkhout, Y.; Eddaoudi, M.; Dong, X. C.; Alshareef, H. N.; Khashab, N. M. Polyoxometalate-cyclodextrin metal-organic frameworks: From tunable structure to customized storage functionality. J. Am. Chem. Soc. 2019, 141, 1847–1851.
Guan, W. M.; Wang, G. X.; Li, B.; Wu, L. X. Organic macrocycle-polyoxometalate hybrids. Coord. Chem. Rev. 2023, 481, 215039.
Li, B.; Wu, L. X. Perspective of polyoxometalate complexes on flexible assembly and integrated potentials. Polyoxometalates 2023, 2, 9140016.
Prochowicz, D.; Kornowicz, A.; Lewiński, J. Interactions of native cyclodextrins with metal ions and inorganic nanoparticles: Fertile landscape for chemistry and materials science. Chem. Rev. 2017, 117, 13461–13501.
Han, Q. X.; He, C.; Zhao, M.; Qi, B.; Niu, J. Y.; Duan, C. Y. Engineering chiral polyoxometalate hybrid metal-organic frameworks for asymmetric dihydroxylation of olefins. J. Am. Chem. Soc. 2013, 135, 10186–10189.
Wang, S. S.; Yang, G. Y. Recent advances in polyoxometalate-catalyzed reactions. Chem. Rev. 2015, 115, 4893–4962.
Hu, G. C.; Chang, W.; An, S.; Qi, B.; Song, Y. F. Self-assembly of reverse micelle nanoreactors by zwitterionic polyoxometalate-based surfactants for high selective production of β-hydroxyl peroxides. Chin. Chem. Lett. 2022, 33, 3968–3972.