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Optically actuating ultra-stable radicals in a large π-conjugated ligand constructed photochromic complex

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Abstract

Producing ultra-stabilized radicals via light irradiation has raised considerable concern but remains a tremendous challenge in functional materials. Herein, optically actuating ultra-stable radicals are discovered in a sterically encumbered and large π-conjugated tri(4-pyridyl)-1,3,5-triazine (TPT) ligands constructed photochromic compound Cu3(H-HEDP)2TPT2-2H2O (QDU-12; HEDP=hydroxyethylidene diphosphonate). The photogeneration of TPT• radicals is the photoactive behavior of electron transfer from HEDP motifs to TPT units. The ultra-long-lived radicals are contributed from strong interchain π-π interactions between the large π-conjugated TPT components, with the radical lifetime maintained for about 18 months under ambient conditions. Moreover, the antiferromagnetic couplings between TPT• radicals and Cu2+ ions plummeted the demagnetization to 35% of its original state after light irradiation, showing the largest room temperature photodemagnetization in the current radical-based photochromic materials.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21901133, 22071125, 22071126, 21571111) and the Key Research and Development Project of Shandong Province (2019GGX102006). We thank for Dr Jian-Hua Qin (Luoyang Normal University, China) for the SCXRD data refinements.

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  1. These authors contributed equally to this work

Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, 266071, China

    Ji-Xiang Hu, Xiao-Fan Jiang, Yu-Juan Ma, Bang-Di Ge, A-Ni Wang, Qi Wei & Guo-Ming Wang

  2. Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an, 710069, China

    Xue-Ru Liu

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  1. Ji-Xiang Hu
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Correspondence to Guo-Ming Wang.

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Hu, JX., Jiang, XF., Ma, YJ. et al. Optically actuating ultra-stable radicals in a large π-conjugated ligand constructed photochromic complex. Sci. China Chem. 64, 432–438 (2021). https://doi.org/10.1007/s11426-020-9891-4

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  • DOI: https://doi.org/10.1007/s11426-020-9891-4

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