Ordered Arrangement of Different Metals in Discrete and Infinite Building Blocks for Heterometallic Metal-Organic Frameworks Construction

Abstract

Construction of sophisticated metal-organic frameworks (MOFs) with multiple kinds of metals is essential for further advancement of porous materials toward various applications. Order and arrangement of the metals in the secondary building units (SBUs) greatly influence the MOF structures outcome. While most of the previous heterometallic MOFs either have multiple kinds of discrete SBUs with different metals, or single kind of SBU with mixed metals inside, other forms of metal distribution still need further exploration. Herein, a bifunctional linker is applied to achieving differential coordination toward different metals. With Ce and Cu serving as the carboxylate-philic and pyrazole-philic metal ions, three heterometallic MOFs (FDM-121—FDM-123) are synthesized. In addition to the common metal arrangement modes, the new MOFs provide a joint reticulation of a discrete SBU and an infinite chain-like SBU featuring different metals in FDM-121, and an assembly from heterometallic infinite chain-like SBU in FDM-122. This study demonstrates the potential of bifunctional linkers for the design and synthesis of heterometallic MOFs and opens up the possibilities to create MOFs with tailored properties for specific applications.

Keywords

Heterometallic / Metal-organic framework / Secondary building unit / Bifunctional

References

[1] Yaghi O M, Li G, Li H. Nature, 1995, 378: 703.

[2] Li H, Eddaoudi M, O’Keeffe M, Yaghi O M. Nature, 1999, 402: 276.

[3] Kitagawa S, Kitaura R, Noro S. Angew. Chem. Int. Ed., 2004, 43: 2334.

[4] Ferey G. Chem. Soc. Rev., 2008, 37: 191.

[5] Zhang J P, Zhang Y B, Lin J B, Chen X M. Chem. Rev., 2012, 112: 1001.

[6] Li B, Wen H M, Cui Y, Zhou W, Qian G. Chen B., Adv. Mater., 201, 28: 8819.

[7] Yuan S, Feng L, Wang K, Pang J, Bosch M, Lollar C, Sun Y, Qin J, Yang X, Zhang P, Wang Q, Zou L, Zhang Y, Zhang L, Fang Y, Li J, Zhou H C. Adv. Mater., 2018, 30: e1704303.

[8] Jiao L, Seow J Y R, Skinner W S, Wang Z U, Jiang H-L. Mater. Today, 2019, 27: 43.

[9] Furukawa H, Cordova K E, O’Keeffe M, Yaghi O M. Science, 2013, 341: 1230444.

[10] Kreno L E, Leong K, Farha O K, Allendorf M, van Duyne R P, Hupp J T. Chem. Rev., 2012, 112: 1105.

[11] Li J R, Sculley J, Zhou H C. Chem. Rev., 2012, 112: 869.

[12] Liu J, Chen L, Cui H, Zhang J, Zhang L, Su C Y. Chem. Soc. Rev., 2014, 43: 6011.

[13] Tranchemontagne D J, Mendoza-Cortes J L, O’Keeffe M, Yaghi O M. Chem. Soc. Rev., 2009, 38: 1257.

[14] Kalmutzki M J, Hanikel N, Yaghi O M. Sci. Adv., 2018, 4: eaat9180.

[15] Li M, Li D, O’Keeffe M, Yaghi O M. Chem. Rev., 2014, 114: 1343.

[16] Kökçam-Demir, Goldman A, Esrafili L, Gharib M, Morsali A, Weingart O, Janiak C. Chem. Soc. Rev., 2020, 49: 2751.

[17] Deria P, Mondloch J E, Tylianakis E, Ghosh P, Bury W, Snurr R Q, Hupp J T, Farha O K. J. Am. Chem. Soc., 2013, 135: 16801.

[18] Tu B, Pang Q, Xu H, Li X, Wang Y, Ma Z, Weng L, Li Q. J. Am. Chem. Soc., 2017, 139: 7998.

[19] Pang Q, Tu B, Li Q. Coord. Chem. Rev., 2019, 388: 107.

[20] Xu W, Tu B, Liu Q, Shu Y, Liang C-C, Diercks C S, Yaghi O M, Zhang Y-B, Deng H, Li Q. Nat. Rev. Mater., 2020, 5: 764.

[21] Qiao J, Liu X, Zhang L, Liu Y. Chem. Res. Chinese Universities, 2022, 381: 31.

[22] Zhang B, Rao Y, Hou L, Liu B, Li Q. ACS Mater. Lett., 2022, 4: 1774.

[23] Yuan S, Qin J S, Li J, Huang L, Feng L, Fang Y, Lollar C, Pang J, Zhang L, Sun D, Alsalme A, Cagin T, Zhou H C. Nat. Commun., 2018, 9: 808.

[24] Martin C R, Leith G A, Kittikhunnatham P, Park K C, Ejegbavwo O A, Mathur A, Callahan C R, Desmond S L, Keener M R, Ahmed F, Pandey S, Smith M D, Phillpot S R, Greytak A B, Shustova N B. Angew. Chem. Int. Ed., 2021, 60: 8072.

[25] Tu B, Diestel L, Shi Z L, Bandara W, Chen Y, Lin W, Zhang Y B, Telfer S G, Li Q. Angew. Chem. Int. Ed., 2019, 58: 5348.

[26] Zhai Q G, Bu X, Mao C, Zhao X, Feng P. J. Am. Chem. Soc., 201, 138: 2524.

[27] López-García C, Canossa S, Hadermann J, Gorni G, Oropeza F E, de l P O V A, Iglesias M, Angeles M M, Gutiérrez-Puebla E, Gándara F. J. Am. Chem. Soc., 2022, 144: 16262.

[28] Bourhis L J, Dolomanov O V, Gildea R J, Howard J A K, Puschmann H. Acta Crystallogr. A, 2015, 71: 59.

[29] Dolomanov O V, Bourhis L J, Gildea R J, Howard J A K, Puschmann H. J. Appl. Crystallogr., 2009, 42: 339.

[30] Sheldrick G. Acta Crystallogr. A, 2015, 71: 3.

[31] Angaridis P A, Baran P, Boča R, Cervantes-Lee F, Haase W, Mezei G, Raptis R G, Werner R. Inorg. Chem., 2002, 41: 2219.

[32] Mezei G, Raptis R G, Telser J. Inorg. Chem., 200, 45: 8841.