Host-Guest [2+2] Cycloaddition Reaction: Postsynthetic Modulation of CO2 Selectivity and Magnetic Properties in a Bimodal Metal-Organic Framework.
Host-Guest [2+2] Cycloaddition Reaction: Postsynthetic Modulation of CO2 Selectivity and Magnetic Properties in a Bimodal Metal-Organic Framework.
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DOI：
10.1002/chem.201505131
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发表时间：
2016-06
期刊：
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通讯作者：
Arpan Hazra;Satyanarayana Bonakala;Karteek K. Bejagam;S. Balasubramanian;T. Maji
中科院分区：
文献类型：
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作者：
Arpan Hazra;Satyanarayana Bonakala;Karteek K. Bejagam;S. Balasubramanian;T. Maji
在金属有机框架中，通过光合成修饰（PSM）同时调谐永久孔隙率和调制磁性能是前所未有的。为了实现这样一种光响应多孔磁性材料，我们合成了一种三维光响应双孔框架MOF1，其二维通道被客体1,2-双（4-吡啶基）乙烯（bpee）、H2 O和EtOH分子占据。1号楼的客人座与柱状座平行排列，乙烯基团之间的距离为3.9 Å；这使得光诱导PSM孔表面通过[2+2]环加成反应产生MOF2。这种光致PSM的框架结构引入了比N2更强的CO2选择性。通过理论计算研究了MOF2比MOF1具有更高的选择性。此外，MOF2揭示了Tc随脱水-再水合反应的可逆变化。这一结果表明，光致PSM是制造新型功能材料的有力工具。
Simultaneous tuning of permanent porosity and modulation of magnetic properties by postsynthetic modification (PSM) with light in a metal-organic framework is unprecedented. With the aim of achieving such a photoresponsive porous magnetic material, a 3D photoresponsive biporous framework, MOF1, which has 2D channels occupied by the guest 1,2-bis(4-pyridyl)ethylene (bpee), H2 O, and EtOH molecules, has been synthesized. The guest bpee in 1 is aligned parallel to pillared bpee with a distance of 3.9 Å between the ethylenic groups; this allows photoinduced PSM of the pore surface through a [2+2] cycloaddition reaction to yield MOF2. Such photoinduced PSM of the framework structure introduces enhanced CO2 selectivity over that of N2 . The higher selectivity in MOF2 than that of MOF1 is studied through theoretical calculations. Moreover, MOF2 unveils reversible changes in Tc with response to dehydration-rehydration. This result demonstrates that photoinduced PSM is a powerful tool for fabricating novel functional materials.