Rare Earth pcu Metal–Organic Framework Platform Based on RE 4 (μ 3 -OH) 4 (COO) 6 2+ Clusters: Rational Design, Directed Synthesis, and Deliberate Tuning of Excitation Wavelengths

Abstract : The Td point group symmetry of rare earth (RE3+) metal clusters RE4(mu3-OH)4(COO)62+ makes them attractive building blocks for creating metal-organic frameworks (MOFs) with controllable topologies. Herein, we describe the design and synthesis of a series of isoreticular MOFs featuring pcu topology [MOF-1114(RE) and MOF-1115(RE)] with variable rare earth metal ions (RE3+ = Y3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+) and linear amino-functionalized dicarboxylate linkers of different lengths. In total, we report 22 MOFs that vary in both composition and structure yet share the same RE4(mu3-OH)4 cluster motif. We demonstrate that these pcu MOFs are cationic and that anion exchange can be used to affect the MOF properties. We also investigate the luminescence properties of a representative member of this MOF series [MOF-1114(Yb)] that exhibits near-infrared emission. We show that the excitation energy for Yb3+ sensitization can be carefully adjusted to lower energy via covalent postsynthetic modification at the amino group sites within the MOF.
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https://hal.archives-ouvertes.fr/hal-01618623
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Submitted on : Wednesday, October 18, 2017 - 11:29:40 AM
Last modification on : Wednesday, April 17, 2019 - 3:00:02 PM

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Tian-Yi Luo, Chong Liu, Svetlana V. Eliseeva, Patrick F. Muldoon, Stéphane Petoud, et al.. Rare Earth pcu Metal–Organic Framework Platform Based on RE 4 (μ 3 -OH) 4 (COO) 6 2+ Clusters: Rational Design, Directed Synthesis, and Deliberate Tuning of Excitation Wavelengths. Journal of the American Chemical Society, American Chemical Society, 2017, 139 (27), pp.9333 - 9340. ⟨10.1021/jacs.7b04532⟩. ⟨hal-01618623⟩

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