基于不同碱基含量的[FeFe]-氢化酶模型化合物功能化聚合物的合成与表征

Synthesis and Characterization of [FeFe]-Hydrogenase Model Complex Functionalized Polymers Based on Different Content of Alkaline Group

将含二炔基的[2Fe2S]模型化合物[Fe2（μ-SCH2C≡CH）2（CO）6]（A）和双叠氮单体2,6-（N3CH2）Py（B,Py=吡啶）与含碱性基团的双炔单体（2-Py CH2）N（CH2C≡CH）2（C,Py=吡啶）通过＂点击反应＂以不同比例进行共聚,得到了6种含不同碱基量的[FeFe]-氢化酶模型化合物功能聚合物Polymer-1～Polymer-6。通过红外光谱、硫元素分析、热重、扫描电镜和电化学对这些聚合物进行了表征。红外光谱和电化学研究表明二铁六羰基单元A以二铁五羰基的形式存在于聚合物中。在共聚过程中,增加单体C的含量能显著改变聚合物的形貌和增加其在有机溶剂中的溶解度,同时热稳定性也有所增加。这些聚合物在含有醋酸的DMF介质中催化质子还原的行为表明,通过单体C引入的碱性基团所形成的次级配位环境对二铁中心的催化性能有显著影响。

Co-polymerization of [2Fe2S] model complex [Fe2（μ-SCH2 C ≡CH）2（CO）6]（A）,diazide 2,6-（N3CH2）Py（B,Py =pyridine） and diyne compound（2-Py CH2）N（CH2C ≡CH）2（C,Py =pyridine） led to the formation of six functionalized Polymers Polymer-1～Polymer-6 via ＂click reaction＂ by varying the ratio of the three components.These Polymers were characterized by IR spectroscopy,sulfur elemental analysis,thermal gravimetric analysis,scanning electron microscopy and electrochemistry.IR spectroscopic data and electrochemical investigations suggested that diiron hexacarbonyl complex A exists as diiron pentacarbonyl unit in these Polymers.In the copolymerizing process,increasing the content of monomer C can significantly change the morphologies of these Polymers and improve their solubility in organic solvents and thermal stability.Electrochemistry of these Polymers in acetic acid-DMF indicated that the secondary coordination atmosphere established by introducing alkaline group provided by the monomer C can significantly enhance the catalytic performance of the diiron units in these Polymers.