Ancillary ligand-regulated Ti(IV)-based metallocalixarene coordination cages for photocatalytic H2 evolution

Yi-Qi Tian; Yun-Shu Cui; Jia-Hui Zhu; Cong-Qiao Xu; Xiao-Yi Yi; Jun Li; Chao Liu

doi:10.1039/d2cc03131k

Ancillary ligand-regulated Ti(IV)-based metallocalixarene coordination cages for photocatalytic H₂ evolution

Chem Commun (Camb). 2022 Aug 9;58(64):9034-9037. doi: 10.1039/d2cc03131k.

Authors

Yi-Qi Tian¹, Yun-Shu Cui², Jia-Hui Zhu¹, Cong-Qiao Xu², Xiao-Yi Yi¹, Jun Li^{2

3}, Chao Liu¹

Affiliations

¹ Hunan Provincial Key Laboratory of Chemical Power Sources, College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, Hunan, P. R. China. chaoliu@csu.edu.cn.
² Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China. xucq@sustech.edu.cn.
³ Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, 100084 Beijing, China.

PMID: 35876039
DOI: 10.1039/d2cc03131k

Abstract

High-valence Ti(IV)-based metallocalixarene coordination cages that are linked by oriented ancillary ligands are unknown so far. Herein, the first family of tunable calixarene-based coordination cages of Ti(IV) with a framework formula [Ti₁₂(OⁱPr)₁₂(TBC[4])₆L₆] have been assembled from six {Ti₂(OⁱPr)₂(TBC[4])}²⁺ nodes and six pyridinedicarboxylic ligands. Furthermore, the {Ti12L6} cage showed strong photocatalytic H₂ evolution activity, and DFT studies were performed to explore its electronic structure.