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Circularly polarized phosphorescence and photon transport of micro/nanocrystals of ruthenium and iridium complexes with chiral anions

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Abstract

Materials with efficient circularly polarized phosphorescences (CPPs) are of potential use in advanced data encryption and anti-counterfeiting, bioimaging, optoelectronic devices and so forth. Herein, a simple method is presented for the preparations of CPP-active micro/nanocrystals with large luminescence dissymmetry factors (glum), high phosphorescence quantum efficiencies (Φp) and tunable emission colors. Diastereomeric IrIII and RuII complexes with chiral (±)-camphorsulfonate counter-anions are readily synthesized and assembled into crystalline microrods, microplates or nanofibers with ordered morphologies. The chir-ality information of chiral counter-anions is efficiently transferred to the metal components to afford CPPs with cyan, green, yellow, or red emission colors and ΦP in the range of 5%–85%. The number of chiral anions is found to play a role in influencing the CPP magnitudes of these crystals. The dicationic RuII and tricationic IrIII complexes show glum values in the 10−2 order, which are much larger with respect to those of monocationic IrIII complexes. Single crystal X-ray analysis is performed to obtain information on the chirality transfer of these materials. In addition, circularly polarized photonic signal waveguiding is demonstrated using the microcrystals of an IrIII complex. This work demonstrates an appealing strategy of constructing chiral micro/nano-architectures for potential applications in chiral nanophotonics.

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Acknowledgements

This work was supported by the Ministry of Science and Technology of China (2022YFA1204401), the National Natural Science Foundation of China (21925112, 22090021) and the BMS Junior Fellow of Beijing National Labortory for Molecular Sciences (BNLMS).

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Zhong-Qiu Li, Zhong-Liang Gong, Tongling Liang, Yu-Wu Zhong & Jiannian Yao

  2. School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, China

    Zhong-Qiu Li, Yu-Wu Zhong & Jiannian Yao

  3. Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania, 15213, USA

    Stefan Bernhard

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  1. Zhong-Qiu Li
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  2. Zhong-Liang Gong
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  4. Stefan Bernhard
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  5. Yu-Wu Zhong
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Correspondence to Yu-Wu Zhong or Jiannian Yao.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors

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11426_2023_1723_MOESM1_ESM.pdf

Circularly Polarized Phosphorescence and Photon Transport of Micro/nanocrystals of Ruthenium and Iridium Complexes with Chiral Anions

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Li, ZQ., Gong, ZL., Liang, T. et al. Circularly polarized phosphorescence and photon transport of micro/nanocrystals of ruthenium and iridium complexes with chiral anions. Sci. China Chem. 66, 2892–2902 (2023). https://doi.org/10.1007/s11426-023-1723-7

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