期刊
CRYSTENGCOMM
卷 14, 期 5, 页码 1819-1824出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2ce06538j
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资金
- Korean Government (MOEHRD) [KRF-2008-331-C00149]
- National Research Foundation of Korea (NRF)
- Ministry of Education, Science and Technology [2011-0008018]
- National Research Foundation of Korea [2011-0008018] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
Topologically interesting new In-MOFs were prepared by using a 4,4'-biphenyldicarboxylate bridging ligand and In(NO3)(3)center dot xH(2)O. Two isomeric forms of In-MOFs were independently prepared and characterized by X-ray crystallography, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), elemental analysis, and gas sorption analysis. By simply using different solvents, N,N-dimethylformamide or N,N-diethylformamide, we obtained two new In-MOFs. Despite the same coordination mode of an In-III node, these two anionic MOFs adopted distinct crystal structures. One isomer (1) showed an overall 4-fold interpenetrated uninodal 4-connected diamond network with Z(t) = 1 and Z(n) = 2 (class IIa). The other (2) showed a 4-fold interpenetrated uninodal 4-connected diamond network with Z(t) = 2 and Z(n) = 2 (class IIIa). Thus, despite the same metal-ligand connectivity, 1 and 2 are unusual isomeric MOFs based on the ways of catenation. This may be accounted for by the flexible bonding nature of the In-centered pseudotetrahedral motif in the presence of counter-cations with different dimensions. The In-MOFs 1 and 2 exhibited different counter ion distributions and porosity properties. Interestingly, the In-MOF 1 showed a reversible framework transformation from crystalline form -> amorphized form (after activation) -> crystalline state (after resolvation). This reversible transformation can also be explained by the flexible bonding nature of the In-III ion with four eta(2)-coordinated 4,4'-BPDC ligands.
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