蒽醌基金属-有机笼光氧化性能

Anthraquinone‑based metal‑organic cages as efficient photocatalysts for oxidation reactions

将光活性蒽醌配体L^(1)和L^(2)(L^(1)=N^(2),N^(7)-双((2,2’-联吡啶)-5-基)-9,10-蒽醌-2,7-双酰胺,L^(2)=N^(2),N^(7)-双(4-((2,2’-联吡啶)-5-基)苯基)-9,10-蒽醌-2,7-双酰胺)与锌离子和亚铁离子通过配位自组装构筑得到一系列配合物1-Zn、2-Zn和2-Fe,单晶X射线衍射和电喷雾质谱等表征表明这一系列配合物为“2+3”的M_(2)L_(3)型金属-有机超分子结构。将蒽醌基金属-有机笼1-Zn与2-Zn应用于甲苯光催化氧化反应中,结果表明笼状催化剂和底物分子间形成超分子主客体化合物是其能有效氧化甲苯的关键。通过对芳香醇的光氧化反应进一步探究1-Zn与2-Zn的光氧化性能,实验结果表明催化产率受到取代基的电子效应和底物分子的尺寸的影响。

Anthraquinone‑based metal‑organic cages 1‑Zn,2‑Zn and 2‑Fe were constructed from ligands L^(1)and L^(2)(L^(1)=N^(2),N^(7)‑di((2,2′‑bipyridin)‑5‑yl)‑9,10‑dioxo‑9,10‑dihydroanthracene‑2,7‑dicarboxamide,L^(2)=N^(2),N^(7)‑bis(4‑((2,2′‑bipyridin)‑5‑yl)phenyl)‑9,10‑dioxo‑9,10‑dihydroanthracene‑2,7‑dicarboxamide)with Zn􀃭and Fe􀃭by coordination self‑assembly.Single crystal X‑ray diffraction and electrospray mass spectrometry showed that this series of complexes were M_(2)L_(3)‑type metal‑organic structures.The 1‑Zn and 2‑Zn supramolecular systems were successfully applied to explore the oxidation of toluene into benzaldehyde,and the experiments suggested that the formation of supramolecular host‑guest compounds between anthraquinone‑based metal‑organic cages and toluene was the key to effective oxidation of toluene.The photooxidation performance of 1‑Zn and 2‑Zn was further investigated by the photooxidation reaction of aromatic alcohols,and the results indicated that the catalytic yields are affected by the electronic effects of the substituents and the size of the substrate molecules.CCDC:2251202,2‑Fe.