Citation: Ying Zhao, Yao He, Jian-Xin Yang, Wen-Jie Liu, Dan Tian, Francisco Aznarez, Le-Le Gong, Li-Long Dang, Lu-Fang Ma. Controllable self-assembly and photothermal conversion of metalla[2]catenanes induced by synergistic effect of free radicals and stacking interactions[J]. Chinese Chemical Letters, ;2025, 36(12): 111460. doi: 10.1016/j.cclet.2025.111460 shu

Controllable self-assembly and photothermal conversion of metalla[2]catenanes induced by synergistic effect of free radicals and stacking interactions

Ying Zhao ^{a, 1} ,
Yao He ^{a, b, 1} ,
Jian-Xin Yang ^a ,
Wen-Jie Liu ^a ,
Dan Tian ^c ,
Francisco Aznarez ^a ,
Le-Le Gong ^{d, *,} ,
Li-Long Dang ^{a, *,} ,
Lu-Fang Ma ^{a, b, *,}

a.
Luoyang Key Laboratory of Green Synthesis and Photofunctional Materials, Luoyang Normal University, Luoyang 471934, China
b.
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China
c.
Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China
d.
State Key Laboratory of NBC Protection for Civilian, Beijing 100191, China

xgllnc@163.com

danglilong8@163.com

mazhuxp@126.com

Received Date: 23 January 2025
Revised Date: 1 June 2025
Accepted Date: 13 June 2025
Available Online: 14 June 2025

Figures(9)

The self-assembly and photothermal application studies of interlocked compounds has been attracting increasing attention during the last decades. Nevertheless, the synthesis of a series of interlocked topologies possessing similar structural characteristic and clarifying their photothermal performance law remains a challenge. Herein, we introduce a new dipyridinyl ligand L1 featuring two methoxy groups, which act as electron-donating species and provide electrons to the central benzene ring, resulting in an enhanced electron rich effect. Previous research indicates that this feature significantly contributes to forming π-stacking interactions. Furthermore, four half-sandwich rhodium-based building blocks exhibiting different metal-to-metal distances and conjugated effect were selected and used to combine with L1 for the synthesis of [2]catenanes and metallamacrocycles for studying the influence of half-sandwich building blocks on photothermal conversion performance under the same accumulation effect. Three new metalla[2]catenanes and one metallamacrocycle have been obtained in high yields and their structure has been unambiguously confirmed by single crystal X-ray diffraction analysis, NMR spectroscopy, and ESI-TOF-MS. In addition, dynamic structural transformation between [2]catenanes and the corresponding metallamacrocycles has been observed through concentration changes and polar solvent induced effect. Photothermal conversion abilities of the isolated complexes were studied and we observed that [2]catenane 3a displayed significant temperature changes (from 25.8 ℃ to 50.3 ℃) under laser irradiation of 1.5 W/cm², thereby reaching a photothermal conversion efficiency of 40.42%. Recorded EPR data indicates that the synergistic cooperation of the free radical effect at the building unit and the stacking effect of [2]catenanes most likely generated photothermal conversion.
- [2]catenanes,
- Structural transformation,
- Coordination-driven self-assembly,
- Supramolecular topologies,
- Photothermal conversion
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