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Thermally Stable Porous Hydrogen‐Bonded Coordination Networks Displaying Dual Properties of Robustness and Dynamics upon Guest Uptake
Author(s) -
Jiang JiJun,
Li Lei,
Lan MeiHua,
Pan Mei,
Eichhöfer Andreas,
Fenske Dieter,
Su ChengYong
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200901929
Subject(s) - monoclinic crystal system , hydrogen bond , microporous material , crystallography , crystallization , adsorption , thermal stability , crystal structure , single crystal , materials science , chemistry , molecule , organic chemistry
Two series of microporous lanthanide coordination networks of the general formula, {[Ln(ntb)Cl 3 ] ⋅ x H 2 O} n (series 1 : monoclinic C 2/ c , Ln=Sm and Tb; series 2 : hexagonal P 3 1 / 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)Cl 3 ] coordination units are consolidated by NH⋅⋅⋅Cl or CH⋅⋅⋅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)Cl 3 ] 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 H 2 , CO 2 , 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.