Two ZnII Metal‐Organic Frameworks with Coordinatively Unsaturated Metal Sites: Structures,Adsorption, and Catalysis |
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| Authors: | Xiao‐Ming Lin Ting‐Ting Li Yi‐Wei Wang Prof. Dr. Li Zhang Prof. Dr. Cheng‐Yong Su |
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| Affiliation: | 1. MOE Laboratory of Bioinorganic and Synthetic Chemistry/KLGHEI of Environment and Energy 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;2. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032 (China) |
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| Abstract: | Assembly of Zn(NO3)2 with the tripodal ligand H3TCPB (1,3,5‐tri(4‐carboxyphenoxy)benzene) affords two porous isoreticular metal‐organic frameworks, [Zn3(TCPB)2?2DEF]? 3DEF ( 1 ) and [Zn3(TCPB)2?2H2O]? 2H2O?4DMF ( 2 ). Single‐crystal X‐ray diffraction analyses reveal that 1 crystallizes in the monoclinic space group P21/c and possesses a 2D network containing 1D microporous opening channels with an effective size of 3.0×2.9 Å2, whereas 2 crystallizes in the trigonal space group  c1 and also possesses a 2D network containing 1D channels, with an effective aperture of 4.0×4.0 Å2. TOPOS analysis reveals that both 1 and 2 have a (3,6)‐connected network topology with the Schläfli symbol of (43?612) (43)2. According to the variable‐temperature powder X‐ray diffraction patterns, the solid phase of 1 can be converted into that of 2 during a temperature‐induced dynamic structural transformation, thus indicating that the framework of 2 represents the most thermally stable polymorph. Desolvated 2 exhibits highly selective adsorption behaviors toward H2/N2, CO2/N2, and CO2/CH4; furthermore, it displays size‐selective catalytic activity towards carbonyl cyanosilylation and Henry (nitroaldol) reactions. |
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| Keywords: | adsorption catalysis Henry reaction metal‐organic frameworks X‐ray diffraction |
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