Citation: Peng Li, Qian-Ru Sun, Chen-Bo Yu, Jia-Li Chen, Yu Zhu, Qian Zhou, Zi-Yan Guo, Shi-Yu Xiong, Jia-Heng Lv, Tian-Yun Fu, Chan Zheng, Qiao-Hong Li, Wei-Hui Fang, Jian Zhang, Dong-Sheng Li. Pyrazole-thermal-assisted assembly of the largest N-rich tin-oxo clusters with tunable broadband nonlinear optical limiting effect[J]. Chinese Chemical Letters, ;2026, 37(9): 111384. doi: 10.1016/j.cclet.2025.111384 shu

Pyrazole-thermal-assisted assembly of the largest N-rich tin-oxo clusters with tunable broadband nonlinear optical limiting effect

Peng Li ^{a, 1} ,
Qian-Ru Sun ^{b, 1} ,
Chen-Bo Yu ^c ,
Jia-Li Chen ^b ,
Yu Zhu ^{a, b, *,} ,
Qian Zhou ^a ,
Zi-Yan Guo ^a ,
Shi-Yu Xiong ^a ,
Jia-Heng Lv ^a ,
Tian-Yun Fu ^a ,
Chan Zheng ^{c, *,} ,
Qiao-Hong Li ^b ,
Wei-Hui Fang ^b ,
Jian Zhang ^b ,
Dong-Sheng Li ^{a, *,}

a.
Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, College of Materials and Chemical Engineering, China Three Gorges University, Yichang 443002, China
b.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
c.
Institute of Biology and Chemistry, Fujian University of Technology, Fuzhou 350118, China

zhuyu@ctgu.edu.cn

czheng@fjut.edu.cn

lidongsheng1@126.com

Received Date: 8 March 2025
Revised Date: 20 May 2025
Accepted Date: 28 May 2025
Available Online: 28 May 2025

Figures(4)

Tin-oxo clusters (TOCs) have attracted considerable attention owing to their various structures and wide potential applications. However, there is still a lack of effective methods to assemble high-nuclearity TOCs. Moreover, the periphery of reported TOCs is rarely N-rich ligands, limiting the comprehensive investigation of the structure-property relationship. In this work, we used the strategy of pyrazole-thermal-assisted organotin aggregation to construct a series of the largest N-rich Sn₁₈ clusters with S₄ axial symmetry. These Sn₁₈ clusters have inorganic electron-withdrawing halogen atoms and organic electron-rich pyrazole derivatives, differing from the reported high-nuclearity TOCs only with carboxylate ligands. Owing to the high symmetry and multiple electron-withdrawing/-donating ligands, the Sn₁₈ clusters served as the platform to investigate the relationship between structure and third-order nonlinear optical (NLO) property by Z-scan measurement. Different from the single organic ligand in the previous study, the multiple kinds of ligands in the Sn₁₈ clusters have an important effect on the NLO property. Enhancing the push-pull electronic effect and introducing C–Cl···π interactions between different ligands can promote the NLO properties. Thus, CTGU-SnC-16 exhibits the best broadband NLO properties at 532 and 1064 nm, differing from the reported metal-oxo clusters only at 532 nm. This work not only affords an effective synthetic strategy for constructing high-nuclearity TOCs but also deepens the understanding of the structure-property relationship of clusters.
- Tin-oxo cluster,
- Pyrazole-thermal synthesis,
- Organic-inorganic hybrid,
- Ligand regulation,
- Optical limiting
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