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Porous Frameworks Based on Carborane–Ln2(CO2)6: Architecture Influenced by Lanthanide Contraction and Selective CO2 Capture

Authors

  • Sheng-Li Huang,

    1. Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, Shanghai 200433 (P. R. China), Fax: (+86) 21-65643776
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    • These authors contributed equally to this work

  • Dr. Yue-Jian Lin,

    1. Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, Shanghai 200433 (P. R. China), Fax: (+86) 21-65643776
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    • These authors contributed equally to this work

  • Wei-Bin Yu,

    1. Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, Shanghai 200433 (P. R. China), Fax: (+86) 21-65643776
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  • Prof. Dr. Guo-Xin Jin

    Corresponding author
    1. Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, Shanghai 200433 (P. R. China), Fax: (+86) 21-65643776
    • Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, Shanghai 200433 (P. R. China), Fax: (+86) 21-65643776
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Abstract

A series of microporous lanthanide coordination polymers containing p-dicarboxylate carborane ligand (18) have been synthesized from the reactions of 1,12-dihydroxycarbonyl-1,12-dicarba-closo-dodecaborane (p-CDCH2) with rare earth metals. Based on the well-known effect of lanthanide contraction, three distinct structure types were isolated: Structure type I crystallizes in the triclinic space group Pequation image with formula {[Ln2(p-CDC)3S6]⋅χS}n (S=solvent molecules, such as H2O, MeOH, and DMF), Ln=Yb3+ (1), Y3+ (2), Tb3+ (3), Gd3+ (4), Sm3+ (6) and structure type II also crystallizes in the triclinic space group Pequation image with formula {[Eu2(p-CDC)3(MeOH)2(H2O)4]⋅[Eu2(p-CDC)3(H2O)4(DMF)2]⋅2DMF}n (5). Nevertheless, structure type III crystallizes in the monoclinic space group P21/n with formula {[Ln2(p-CDC)3(MeOH)4(DMF)2]⋅2 MeOH}n, Ln=Ce3+ (7) and La3+ (8). The structures of type I polymers consist of four-connected 2D lamellar networks, but type II and type III polymers are composed of six-connected 3D structures. Gas sorption property of compound 1’ was studied, which showed selective CO2 capture over CH4 and N2.

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