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Arylazopyrazole-functionalized photoswitchable octanuclear Zn(II)-silsesquioxane nanocage

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Abstract

Photoswitchable organic materials have shown significant advancement for photonic applications, however, the polynuclear metal clusters conjugated with photoswitching properties are still formidable. Herein, a novel octanuclear Zn(II) nanocage {[Zn8-(Me4Si4O8)2(azopz)8]·4CH2Cl2·MeOH·MeCN} (SD/Zn8) (Hazopz=3,5-dimethyl-4-(phenyldiazenyl)-1H-pyrazole), based on multidentate silsesquioxane and pyrazole modified by photoisomerizable azo group has been designed and synthesized to realize the reversible photoswitching behavior. X-ray crystallographic study reveals that the unique metal core consists of two annular Me4Si4O84− sandwiching a ring of eight Zn atoms where the pyrazole end of azopz− bridges them together. The azopz− ligands diverge above and below the plane defined by eight Zn atoms. Importantly, SD/Zn8 shows quick trans-to-cis transformation upon 365 nm light irradiation, which can be easily changed back by 450 nm light, but slow cis-to-trans reversibility at room temperature as confirmed by UV-Vis and 1H NMR spectroscopies. This process, which presumably regulates the spaces, acts like a pump and is completely repetitive. As such, it can be considered as a molecular pump energized by light. Importantly, the molecule is an energy reservoir where it absorbs the light energy and releases it slowly with time.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (91961105, 21822107, 21571115, 21827801), the Natural Science Foundation of Shandong Province (ZR2019ZD45, JQ201803, ZR2017MB061), the Taishan Scholar Project of Shandong Province of China (tsqn201812003, ts20190908), the Qilu Youth Scholar Funding of Shandong University, the Project for Scientific Research Innovation Team of Young Scholar in Colleges and Universities of Shandong Province (2019KJC028, 2019KJJ009) and the State Key Laboratory of Pollution Control and Resource Reuse Foundation (PCRRF18019).

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Authors and Affiliations

  1. School of Aeronautics, Shandong Jiaotong University, Ji’nan, 250037, China

    Kai Sheng

  2. School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Ji’nan, 250100, China

    Ya-Nan Liu, Rakesh Kumar Gupta & Di Sun

  3. Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, 252000, China

    Di Sun

  4. Institut de Chimie de Strasbourg, Universite de Strasbourg, CNRS-UMR 7177, 4 rue Blaise Pascal, Strasbourg Cedex, 67008, France

    Mohamedally Kurmoo

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  1. Kai Sheng
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  2. Ya-Nan Liu
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  3. Rakesh Kumar Gupta
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  4. Mohamedally Kurmoo
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Correspondence to Rakesh Kumar Gupta or Di Sun.

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Sheng, K., Liu, YN., Gupta, R.K. et al. Arylazopyrazole-functionalized photoswitchable octanuclear Zn(II)-silsesquioxane nanocage. Sci. China Chem. 64, 419–425 (2021). https://doi.org/10.1007/s11426-020-9886-5

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