@article{Zhao2025, 
author = {Qing Zhao and Dong-Ao Mao and Liang-Liang Huang and Kun Zhou and Hong-Rui Tian and Bao-Kuan Chen and Yan-Feng Bi},
title = {Thiacalix[4]arene-functionalized molecular clusters involving the Keggin-type PM4Mo8 (M = Co, Ni) motif: Electrochemical and photothermal conversion properties},
year = {2025},
journal = {Polyoxometalates},
volume = {4},
number = {3},
pages = {9140091},
keywords = {photothermal conversion, thiacalix[4]arene, electrochemical property, Keggin-type polyoxometalate},
url = {https://www.sciopen.com/article/10.26599/POM.2025.9140091},
doi = {10.26599/POM.2025.9140091},
abstract = {Herein, four new thiacalixarene-functionalized polyoxometalate clusters, [Na2.5(H2O)2.5Co4(TC4A)PMo8O32][(CH3)2NH2]4.5(CH3OH)(DMF)1.5(H2O) (PCo4Mo8 (1), H4TC4A = p-tert-butylthiacalix[4]arene), [H4Ni4(TC4A)PMo8O32][(CH3)2NH2]3(DMF)4(CH3OH)2(H2O)2 (PNi4Mo8 (2)), and [M4(TC4A)PMo8VO33][N(CH3)4]2[HN(CH3)3][(CH3)2NH2](DMF)2(CH3OH)5 (M = Co, PCo4Mo8V (3); M = Ni, PNi4Mo8V (4)), were synthesized under solvothermal conditions and characterized using single-crystal X-ray diffraction. These four clusters were found to contain Keggin-type PM4Mo8 motifs, exhibiting redox properties similar to those of PMo12O403− (PMo12), superior structural stability, and the ability to electrocatalytically reduce IO3−. The substitution of the four metal ions, along with the capping with the TC4A ligand and VO unit, considerably modulated the visible-light absorption of the clusters, enhancing the photothermal conversion in the solid-state and organic solutions. The efficiency of the photothermal conversion revealed that the absorption of visible light relies on electron transfer pathways, which were elucidated through band gap analysis, density functional theory calculations, and X-ray photoelectron spectroscopy.}
}