Thermally Stable Porous Hydrogen-Bonded Coordination Networks Displaying Dual Properties of Robustness and Dynamics upon Guest Uptake

Authors

  • Ji-Jun Jiang,

    1. MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry & Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (China), Fax: (+86) 20-8411-5178
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  • Lei Li,

    1. MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry & Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (China), Fax: (+86) 20-8411-5178
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  • Mei-Hua Lan,

    1. MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry & Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (China), Fax: (+86) 20-8411-5178
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  • Mei Pan,

    1. MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry & Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (China), Fax: (+86) 20-8411-5178
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  • Andreas Eichhöfer Dr.,

    1. Institut für Nanotechnologie, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe (Germany)
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  • Dieter Fenske Prof.,

    1. Institut für Nanotechnologie, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe (Germany)
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  • Cheng-Yong Su Prof.

    1. MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry & Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (China), Fax: (+86) 20-8411-5178
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Abstract

Two series of microporous lanthanide coordination networks of the general formula, {[Ln(ntb)Cl3]x H2O}n (series 1: monoclinic C2/c, Ln=Sm and Tb; series 2: hexagonal P31/c, Ln=Sm and Eu; ntb=tris(benzimidazol-2-ylmethyl)amine, x=0–4) have been synthesized and characterized by IR, elemental analyses, thermal gravimetry, and single-crystal and powder X-ray diffraction methods. In both series, the monomeric [Ln(ntb)Cl3] coordination units are consolidated by N[BOND]H⋅⋅⋅Cl or C[BOND]H⋅⋅⋅Cl hydrogen bonds to sustain three-dimensional (3D) networks. However, the different modes of hydrogen bonding in the two series lead to crystallization of the same [Ln(ntb)Cl3] monomers in different forms (monoclinic vs. hexagonal), consequently giving rise to distinct porous structures. The resulting hydrogen-bonded coordination networks display high thermal stability and robustness in water removal/inclusion processes, which was confirmed by temperature-dependent single-crystal-to-single-crystal transformation measurements. Adsorption studies with H2, CO2, and MeOH have been carried out, and reveal distinct differences in adsorption behavior between the two forms. In the case of MeOH uptake, the monoclinic network shows a normal type I isotherm, whereas the hexagonal network displays dynamic porous properties.

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