Abstract
N-doping has significant influence in manipu-lating the properties of TiO2,and this has stimulated the development of N-donor-functionalized titanium-oxo clusters(TOCs)as molecular models to study the struc-ture-property relationship.However,the structural type and photoresponsive application are still limited for such TOCs,especially regarding the high-nuclearity TOCs that contain structure unit of TiO2 for photocatalysis.Herein,we showed the synthesis of a series of high-nuclearity TOCs 1-3 compounds using π-conjugated 1,10-phenan-throline(phen)as chromophore and N-donor functional ligand.Compound 1 features cocrystal structure composed of one[Ti26]2+and half[Ti22]2+,which renders it as the first cocrystallized TOC containing two positively charged species and phen-functionalized TOC showing the highest nuclearity up to 37 Ti centers.By adjusting the synthetic conditions,the individual {Ti22} and(Ti26} clusters can also be isolated as Compounds 2 and 3,respectively.The core structure of {Ti22} is mainly constructed from four lacunary {Ti4} derived from pentagonal {Ti(Ti)5} unit,while {Ti26} is built from four complete {Ti(Ti)5} unit.Notably,a {Ti8O14} structure unit of anatase TiO2 can be identified in {Ti26}.Based on the unique structural features and proper photophysical and photochemical properties of Compounds 1-3,they are applied for photocatalytic sul-foxidation.Owing to the presence of anatase structure unit in {Ti26} and the synergistic effect from {Ti22} and {Ti26},the catalytic performance presents in the order of Com-pound 1＞Compound 3＞Compound 2.This work pro-vides excellent models to understand the structure-property relationship from the perspective of cocrystal-lization and Ti-O binding model and will further promote the application of TOCs as functional catalysts for organic transformation.
基金项目
National Natural Science Foundation of China(21901037)
National Natural Science Foundation of China(21901038)
National Natural Science Foundation of China(92161111)
Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning()
Fundamental Research Funds for the Central Universities(2232019G-07)
International Cooperation Fund of Science and Technology Commission of Shanghai Municipality(21130750100)
NETL
NSTL
万方数据