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Different molecular conformation and packing determining mechanochromism and room-temperature phosphorescence

不同分子构象与堆积决定力致变色与室温磷光性能

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Abstract

The phenomenon that different molecular packing modes in aggregates result in different optical properties has attracted intense attention, since it can provide useful information to establish the relationship between the micro- and macro-world. In this paper, DBTDO-DMAC was designed with 9,10-dihydro-9,9-dimethylacridine (DMAC) as electron donor. DBTDO-DPA and DBTDO-Cz were designed for comparison, which adopted diphenylamine (DPA) with twisted structure and carbazole (Cz) with planar structure as donors, respectively. As expected, two polymorphs (Crystal G and Crystal Y) of DBTDO-DMAC were obtained and exhibited distinct properties. Crystal G originating from planar conformation exhibited mechanochromism (MC) phenomenon and the emission color changed from green to yellow with a redshift of 35 nm after grinding. Nevertheless, Crystal Y with folded conformation displayed obvious room-temperature phosphorescence (RTP) with yellow afterglow. Careful single crystal analyses, powder X-ray diffraction and theoretical calculation reveal that the different emissive behaviors are highly related to the molecular conformation and packing modes. The successful adjustment of molecular conformation provides some guidance in the design of other MC and/or RTP luminogens, broadens the molecule family with the tunable molecular conformation and opens up a new avenue for exploring possible adjustment of molecular packing in aggregates.

摘要

本文设计并合成了DBTDO-DMAC, 以及两个对比分子DBTDO-DPA和DBTDO-Cz, 证明了分子堆积形式对发光性能的影响. 其中, DBTDO-DMAC具有两种不同的晶型: 晶体G表现出明显的力致变色(MC)现象, 研磨前后的荧光由绿色变为黄色, 光谱红移35 nm; 晶体Y表现出明显的黄色室温磷光(RTP)现象. 为进一 步探究这种差异的内在机理, 结合单晶结构、 粉末XRD和理论计 算等对其进行了详细分析, 结果表明分子不同的发光行为与分子构象和堆积方式密切相关. 这种调节聚集态分子排列的方式, 为其他MC和/或RTP发光材料的设计提供了指导, 成为进一步优化调节有机、 高分子功能材料性能的又一重要手段, 再次表明MUSIC概念的重要性.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21875130), the Starting Foundation of Tianjin University and the Project of “100 Talents Program” of Shanxi Province.

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan, 030006, China

    Shuhui Li  (李姝慧) & Heping Shi  (施和平)

  2. Institute of Molecular Aggregation Science, Tianjin University, Tianjin, 300072, China

    Shuhui Li  (李姝慧), Yujun Xie  (谢育俊), Aisen Li  (李爱森), Xiaoning Li  (李晓宁), Weilong Che  (车伟龙), Jinfeng Wang  (王金凤) & Zhen Li  (李振)

  3. Department of Chemistry, Wuhan University, Wuhan, 430072, China

    Zhen Li  (李振)

  4. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, 350207, China

    Zhen Li  (李振)

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  1. Shuhui Li  (李姝慧)
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  2. Yujun Xie  (谢育俊)
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  3. Aisen Li  (李爱森)
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  4. Xiaoning Li  (李晓宁)
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  6. Jinfeng Wang  (王金凤)
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  7. Heping Shi  (施和平)
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  8. Zhen Li  (李振)
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Contributions

Author contributions Wang J, Shi H and Li Z designed the whole work; Li S synthesized all compounds, grew and measured the crystals; Li S characterized the photo-physical properties with the help from Li X and Che W; Li S and Li A performed the data analysis; Xie Y performed the theoretical calculations; Li S wrote the paper with support from Wang J, Shi H and Li Z. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Jinfeng Wang  (王金凤), Heping Shi  (施和平) or Zhen Li  (李振).

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Conflict of interest The authors declare no conflict of interest.

Additional information

Shuhui Li received her BSc degree from Shanxi University in 2018. Now she is a Master student at the School of Chemistry and Chemical Engineering, Shanxi University. Her research interests focus on novel luminescent materials with stimuli-responsive fluorescence, room-temperature phosphorescence, and thermally activated delayed fluorescence properties.

Jinfeng Wang received her BSc degree from Hubei University in 2014 and her PhD degree from Wuhan University in 2019. She has been working at Tianjin University since 2019. Her research interests are in dye-sensitized solar cells, mechanoluminescence and room-temperature phosphorescence.

Heping Shi received his BSc degree from Taiyuan Normal University in 1991 and his PhD degree from Shanxi University in 2004. He has been working at Shanxi University since 1997. He was a visiting scholar at the Hong Kong University of Science and Technology from 2014 to 2015 and at the University of Melbourne from 2016 to 2017. His research interests are in aggregation-induced emission materials and thermally activated delayed fluorescence materials.

Zhen Li received his BSc and PhD degrees from Wuhan University in 1997 and 2002, respectively. He has been a full Professor at Wuhan University since 2006 and Chair Professor at Tianjin University since 2018. His research interests are in the development of organic molecules and polymers with new structures and functions for organic electronics and photonics.

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Li, S., Xie, Y., Li, A. et al. Different molecular conformation and packing determining mechanochromism and room-temperature phosphorescence. Sci. China Mater. 64, 2813–2823 (2021). https://doi.org/10.1007/s40843-021-1658-9

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