π-conjugated chromophore functionalized high-nuclearity titanium-oxo clusters containing structural unit of anatase for photocatalytic selective oxidation of sulfides  

作　　者：Ling-Rong Liao Dong-Chun Zheng Pin-Xi Ou Qi-Xin Zhao Wei-Min Xuan Qi Zheng 

机构地区：[1]State Key Laboratory for Modification of Chemical Fibers and Polymer Materials&College of Materials Science and Engineering,Donghua University,Shanghai,201620,China [2]State Key Laboratory for Modification of Chemical Fibers and Polymer Materials and College of Chemistry and Chemical Engineering,Donghua University,Shanghai 201620,China

出　　处：《Rare Metals》2024年第4期1736-1746,共11页稀有金属（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(Nos.21901037,21901038 and 92161111);the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning;the Fundamental Research Funds for the Central Universities(No.2232019G-07);the International Cooperation Fund of Science and Technology Commission of Shanghai Municipality(No.21130750100)。

摘　　要：N-doping has significant influence in manipulating the properties of TiO_(2),and this has stimulated the development of N-donor-functionalized titanium-oxo clusters(TOCs)as molecular models to study the structure-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 TiO_(2)for photocatalysis.Herein,we showed the synthesis of a series of high-nuclearity TOCs 1-3 compounds usingπ-conjugated 1,10-phenanthroline(phen)as chromophore and N-donor functional ligand.Compound 1 features cocrystal structure composed of one[Ti_(26)]~(2+)and half[Ti_(22)]~(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{Ti_(22)}and{Ti_(26)}clusters can also be isolated as Compounds 2 and 3,respectively.The core structure of{Ti_(22)}is mainly constructed from four lacunary{Ti_(4)}derived from pentagonal{Ti(Ti)_5}unit,while{Ti_(26)}is built from four complete{Ti(Ti)_5}unit.Notably,a{Ti_8O_(14)}structure unit of anatase TiO_(2)can be identified in{Ti_(26)}.Based on the unique structural features and proper photophysical and photochemical properties of Compounds 1-3,they are applied for photocatalytic sulfoxidation.Owing to the presence of anatase structure unit in{Ti_(26)}and the synergistic effect from{Ti_(22)}and{Ti_(26)},the catalytic performance presents in the order of Compound 1>Compound 3>Compound 2.This work provides excellent models to understand the structureproperty relationship from the perspective of cocrystallization and Ti-O binding model and will further promote the application of TOCs as functional catalysts for organic transformation.

关 键 词：Titanium-oxo cluster Molecular model of anatase TiO_(2) High nuclearity π-conjugated chromophore Photocatalytic sulfoxidation 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]