异硫氰酸荧光素后修饰的金属有机三元环光解水制氢

将具有N、O、P三齿配位点的直线型双臂席夫碱配体L1与钴离子配位自组装得到一例3+3]金属-有机三元环Co-L1。在该配体的苯环侧链上引入易于修饰的NH₂基团，通过组装后修饰的方法把光活性的异硫氰酸荧光素（FITC）分子以共价键方式键合到金属-有机三元环上，并将其用于可见光下的光解水制氢。该体系属于无须引入额外光敏剂的双组分放氢体系。与传统的三组分体系相比，在同等金属催化剂和光敏剂浓度下，组装后修饰的金属配合物催化剂Co-L3具有更高的光催化活性，转换数（TON）可以达到80，大约是Co-L1光催化效率的30倍。

Photocatalytic Hydrogen Production Based on Metal-Organic Triangle Modified by Fluorescein Isothiocyanate

A cobalt based metal-organic3+3] self-assembly macrocycle was constructed by tridentate Schiff base ligand L1 with N, O and P atoms (L1=1,1''-biphenyl-4,4''-di-carbohydrazide-bis-(2-diphenyphosphinobenzaldehyde)). The functionalized metal-organic triangle with amino groups was connected to photoactive fluorescein isothiocyanate (FITC) via post-assembly modification reaction. This modified complex Co-L3 was used as photocatalyst for hydrogen evolution from water splitting. It was a two-component system for hydrogen production without extra photosensitizer. Besides, compared with the three-component system, the metallosupramolecular catalyst Co-L3 underwent post-assembly modification reactions exhibited higher photocatalytic activity at the same metal catalyst and photosensitizer concentration with a turnover number (TON) of 80, which was approximately 30 times the photocatalytic efficiency of complex Co-L1.