氧杂蒽染料修饰钴-硫脲配合物的光解水放氢性能（英文）

Photocatalytic Hydrogen Production Based on Cobalt-Thiosemicarbazone Complex with the Xanthene Dye Moiety

将具有不同端基的硫脲基团与三苯基磷组分结合,利用所得到的配体合成了2个具有NSP(氮硫磷)鳌合位点的钴-硫脲化合物,并研究了其光解水产氢性能。配合物[Co(L2)(L2′)](BF_4)_(2.5)·H_2O·0.5C_2H_5OH(2)(L2=(2-二苯基膦-苯烯基)-氨基硫脲腙-罗丹明6G,L2′=(2-二苯基膦氧-苯烯基)-氨基硫脲腙-罗丹明6G)通过引入罗丹明荧光团与光敏剂分子协同作用,其产氢TON值可以达到2 800 molH2·molcat^(-1),其初始TOF值可达到930 molH_2·molcat^(-1)·h^(-1)。相同条件下,相比于配合物[Co(L1)(L1′)](BF_4)·0.5H_2O(1)(L1=(2-二苯基膦-苯烯基)-氨基硫脲腙-硫甲基,L1′=(2-二苯基膦氧-苯烯基)-氨基硫脲腙-硫甲基),提高了体系的催化活性,可能是由于荧光素分子与配合物2之间的分子间π-π堆积作用有利于光敏剂和光催化剂之间的光致电子转移。

Two cobalt complexes containing NSP （nitrogen-sulphur-phosphor） chelator prepared from thiose-micarbazone ligands with different terminal functional groups and triphenylphosphine moiety have been synthesized in high yield and characterized. Their photocatalytic activity for hydrogen evolution under visible light irradiation was investigated. The photocatalyst [Co（L2）（L2＇）]（BF4）2.5·H2O·0.5C2H5OH （2） （L2=2-（diphenylphosphino）benzylidene-2-（3, 6-bis（ethylamino）-2, 7-dimethyl-9H-xanthen-9-yl）benzothiohydrazide, L2＇=2-（diphenylphosphinooxide）benzylidene-2-（3, 6-bis（ethylamino）-2, 7-dimethyl-9H-xanthen-9-yl） benzothiohydrazide） containing rhodamine groups exhibited activity in light driven hydrogen evolution with the TON and initial TOF reaching to 2 800 molH2·molcat-1 and 930 molH2·molcat-1·h-1, respectively, which is much higher than that of complex [Co（L1）（L1＇）]（BF4）·0.5H2O （1） （L1=2-（diphenylphosphino）benzylidene hydrazinecarbodithionate, L1＇=2-（diphenyl-phosphinooxide）benzylidene hydrazinecarbodithionate） under similar conditions. The higher catalytic activity was attributed to the potential intermolecular π-π stack interactions between the catalyst 2 and photosensitizer fluorescein （Fl） benefiting the photoinduced electron transfer between the photosensitizer and the photocatalyst.