Issue 5, 2023

The tail of imidazole regulated the assembly of two robust sandwich-type polyoxotungstate-based open frameworks with efficient visible-white-light-driven catalytic oxidation of sulfides

Abstract

Visible-white-light-driven selective aerobic oxidation of sulfides is highly attractive but challenging for modern organic and pharmaceutical synthesis. Thus, there is an urgent need for exploiting high-performance photocatalytic systems to reform the value-added organic transformation. Herein, we elucidated a bottom-up strategy to construct two robust zinc-imidazole metal–organic linker extended sandwiched-type polyoxotungstate-based open frameworks (POTOFs), {[Zn(1-pIM)3]2[Zn6(AsW9O33)2(1-pIM)6]·2(1-HpIM)·2H2O}n (LCU-20) and {[Zn(1-ipIM)3]2[Zn6(SbW9O33)2(1-ipIM)6]·2(1-HipIM)}n (LCU-21) (1-pIM = 1-propylimidazole, 1-ipIM = 1-isopropylimidazole) by tuning the substituent tails outside the imidazole. Interestingly, LCU-20 and LCU-21 exhibit 2D sql and 3D 2-fold interpenetrated lvt networks, respectively, although both nodes in LCU-20 and LCU-21 are similar 4-connected Zn6 ring seamed trivacant polyoxotungstate anions. Interestingly, the substituent tails of imidazole instead of the heteroatom in polyoxotungstates play a key role in determining the network propagation orientation that dictates the dimensionality of the final network of POTOFs. More importantly, the alliance of sandwich-type polyanions and zinc-imidazole metal–organic units can produce metal-to-metal charge transfer (MMCT) chromophores, endowing them with visible-light responsive features. Therefore, benefiting from the oxidative active species of O2˙ and h+, LCU-20 exhibits efficient heterogeneous catalytic activities for the oxidation of sulfides with high yield (∼99%) and excellent selectivity (∼99%) under visible-white-light irradiation (>600 nm) in the ambient environment. This work not only presents a new approach for the construction of 3D POTOFs but also describes the white-light-driven oxidation of sulfides catalyzed by this type of material.

Graphical abstract: The tail of imidazole regulated the assembly of two robust sandwich-type polyoxotungstate-based open frameworks with efficient visible-white-light-driven catalytic oxidation of sulfides

Supplementary files

Article information

Article type
Research Article
Submitted
03 Jän 2023
Accepted
01 Feb 2023
First published
01 Feb 2023

Inorg. Chem. Front., 2023,10, 1465-1474

The tail of imidazole regulated the assembly of two robust sandwich-type polyoxotungstate-based open frameworks with efficient visible-white-light-driven catalytic oxidation of sulfides

X. Huang, S. Liu, Z. Zhou, H. Zhang, Z. Gao, G. Shen, H. Wang, Z. Wang, Q. Yao and D. Sun, Inorg. Chem. Front., 2023, 10, 1465 DOI: 10.1039/D3QI00018D

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