A porous and redox active ferrocenedicarboxylic acid based aluminium MOF with a MIL-53 architecture.
A porous and redox active ferrocenedicarboxylic acid based aluminium MOF with a MIL-53 architecture.
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DOI：
10.1039/c9dt03489g
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发表时间：
2019-11
影响因子：
4
通讯作者：
Jan Benecke;Sebastian Mangelsen;Tobias A. Engesser;Thomas Weyrich;Jannik Junge;N. Stock;H. Reinsch
中科院分区：
文献类型：
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作者：
Jan Benecke;Sebastian Mangelsen;Tobias A. Engesser;Thomas Weyrich;Jannik Junge;N. Stock;H. Reinsch
采用茂金属连接剂1,1′-二茂铁二羧酸（H2FcDC）合成了第一个具有MIL-53结构的永久多孔二茂铁二羧酸盐。该化合物Al- mil -53-FcDC [Al(OH)(FcDC)]在≤100°C的温和合成条件下，经过90分钟的短反应时间，在玻璃小瓶中得到。通过粉末x射线衍射数据确定了该化合物的晶体结构，该化合物对N2和H2O有孔隙，BET比表面积为340 m2 g-1。通过EPR和Mössbauer光谱对MOF进行了表征。Al-MIL-53-FcDC的Mössbauer谱线显示出同分异构体位移为0.34 mm s-1的特征双重态和2.39 mm s-1的四极分裂，证明了二茂铁部分的持久性。作为一种补充技术，EPR光谱可以检测到微量的二茂铁离子杂质。循环伏安实验证实了Al-MIL-53-FcDC中连接分子FcDC2-的可达氧化还原活性。FcDC2-的可逆氧化和还原信号（分别为0.75 V和0.64 V vs. Ag）在40个CV循环中保持，而MOF的结晶度在实验结束后保持不变。
A metallocene based linker 1,1'-ferrocenedicarboxylic acid (H2FcDC) was used to synthesise the first permanently porous ferrocenedicarboxylate, exhibiting a MIL-53 architecture. This compound Al-MIL-53-FcDC [Al(OH)(FcDC)] is obtained in glass vials under mild synthesis conditions at ≤100 °C and after a short reaction time of 90 min. The crystal structure was determined from powder X-ray diffraction data and the compound shows porosity towards N2 and H2O, exhibiting a BET surface area of 340 m2 g-1. Furthermore, the MOF was characterised via EPR and Mössbauer spectroscopy. The Mössbauer spectrum of Al-MIL-53-FcDC shows a characteristic doublet with an isomeric shift of 0.34 mm s-1 and a quadrupole splitting of 2.39 mm s-1, proving the persistence of the ferrocene moiety. A negligibly small amount of impurities of ferrocenium ions could be detected by EPR spectroscopy as a complementary technique. Cyclic voltammetric experiments demonstrated the accessible redox activity of the linker molecule FcDC2- in Al-MIL-53-FcDC. A reversible oxidation and reduction signal (0.75 V and 0.64 V, respectively, vs. Ag) of FcDC2- was observed and maintained during forty CV cycles, while the crystallinity of the MOF remained unchanged after the experiment.