Assembly of Homochiral Titanium-Oxo Clusters Protected by in situ Generated Chiral Ligands for Enhanced Photoelectrochemical Activity
Nahui Huang
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
† These authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Jinle Hou
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
† These authors contributed equally to this work.
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorYe Wang
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
Search for more papers by this authorPengfei Fei
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
Search for more papers by this authorDongxu Zhang
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
Search for more papers by this authorZhi Wang
School of Chemistry and Chemical Engineering, Shandong University, Jinan, Shandong, 250100 China
Search for more papers by this authorKonggang Qu
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
Search for more papers by this authorCorresponding Author
Xianxi Zhang
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorCorresponding Author
Di Sun
School of Chemistry and Chemical Engineering, Shandong University, Jinan, Shandong, 250100 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorNahui Huang
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
† These authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Jinle Hou
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
† These authors contributed equally to this work.
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorYe Wang
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
Search for more papers by this authorPengfei Fei
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
Search for more papers by this authorDongxu Zhang
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
Search for more papers by this authorZhi Wang
School of Chemistry and Chemical Engineering, Shandong University, Jinan, Shandong, 250100 China
Search for more papers by this authorKonggang Qu
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
Search for more papers by this authorCorresponding Author
Xianxi Zhang
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong, 252000 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorCorresponding Author
Di Sun
School of Chemistry and Chemical Engineering, Shandong University, Jinan, Shandong, 250100 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorComprehensive Summary
The synthesis of titanium oxo clusters (TOCs) with both chirality and photoactivity is urgently needed to expand their applications. However, this remains a significant challenge due to synthetic difficulties and limitations in chiral ligand selection. In this work, we have isolated two pairs of enantiomeric TOCs, [Ti3(μ3-O)(R/S-L1)2(iPrO)6] (R/S-Ti3; iPrOH = isopropanol, R/S-L1 = R/S-2'-hydroxy-[1,1'- binaphthalen]-2-yl isopropyl hydrogenphosphate) and [Ti4(μ2-O)(μ4-O)(R/S-L2)2(EtO)8] (R/S-Ti4; EtOH = ethanol, R/S-L2 = R/S-2'-hydroxy-[1,1'-binaphthalen]-2-yl ethyl hydrogenphosphate), via an in situ ligand transformation approach. The R/S-L1 and R/S-L2 ligands were obtained by alcoholysis of R/S-L (R/S-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate) in different reaction solvents. These ligands, with additional coordination sites, facilitated the formation of novel TOCs and improved their stability. Importantly, these clusters exhibited exceptional stability in solid state and maintained appreciable stability in solution. Furthermore, the introduction of chiral ligands not only imparts a homochiral nature to R/S-Ti3 and R/S-Ti4 but also confers upon them superior photoelectric properties due to ligand-to-metal charge transfer (LMCT) phenomena, as confirmed by theoretical calculations. This study offers a valuable synthetic strategy for preparing photoactive chiral TOCs, and we anticipate it will inspire new discoveries in the field of chiral metal nanoclusters.
Supporting Information
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