Accurately adjusted phenothiazine conformations: reversible conformation transformation at room temperature and self-recoverable stimuli-responsive phosphorescence

Yuan Gao; Wentao Yuan; Yuexin Li; Arui Huang; Yuanyuan Fang; Aisen Li; Kai Wang; Bo Zou; Qianqian Li; Zhen Li

doi:10.1038/s41377-024-01716-7

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Accurately adjusted phenothiazine conformations: reversible conformation transformation at room temperature and self-recoverable stimuli-responsive phosphorescence

Original Articles

- Accurately adjusted phenothiazine conformations: reversible conformation transformation at room temperature and self-recoverable stimuli-responsive phosphorescence
- Light: Science & Applications Vol. 14, Issue 4, Pages: 1002-1015(2025)
- Affiliations：
  
  1.Hubei Key Lab on Organic and Polymeric Opto-Electronic Materials, Department of Chemistry, Wuhan University, Wuhan 430072, China
  2.State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012, China
  3.School of Physical Science and Information Technology, Liaocheng University, Liaocheng 252059, China
  4.TaiKang Center for Life and Medical Sciences, Wuhan University, Wuhan 430072, China
- Author bio：
  
  Qianqian Li (liqianiqian@whu.edu.cn)
- Funds：
- DOI：10.1038/s41377-024-01716-7
  CLC：
- Received：09 August 2024，
  
  Revised：27 November 2024，
  
  Accepted：2024-12-05，
  
  Published Online：26 February 2025，
  
  Published：30 April 2025
- Accepted：
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Gao, Y. et al. Accurately adjusted phenothiazine conformations: reversible conformation transformation at room temperature and self-recoverable stimuli-responsive phosphorescence. Light: Science & Applications, 14, 1002-1015 (2025).
DOI：

Gao, Y. et al. Accurately adjusted phenothiazine conformations: reversible conformation transformation at room temperature and self-recoverable stimuli-responsive phosphorescence. Light: Science & Applications, 14, 1002-1015 (2025). DOI： 10.1038/s41377-024-01716-7.

摘要

Abstract

Conformational flexibility is essential to the stimuli-responsive property of organic materials

but achieving the reversible molecular transformation is still challenging in functional materials for the high energy barriers and restriction by intermolecular interactions. Herein

through the incorporation of various steric hindrances into phenothiazine derivatives with different positions and quantities to tune the molecular conformations by adjustable repulsive forces

the folded angles gradually changed from 180° to 90° in 17 compounds. When the angle located at 112° with moderated steric effect

dynamic and reversible transformation of conformations under mechanical force has been achieved for the low energy barriers and mutually regulated molecular motions

resulting in both self-recoverable and stimuli-responsive phosphorescence properties for the first time. It opened up a new way to realize the self-recovery property of organic materials

which can facilitate the multi-functional property of smart materials with the opened avenue for other fields with inspiration.

关键词

Keywords

references

Gao, Y. et al. Thermal annealing promoted room temperature phosphorescence: motion models and internal mechanism. Natl Sci. Rev. 10 , nwad239 (2023)..

Cen, S. Y. et al. Conformational enantiodiscrimination for asymmetric construction of atropisomers. Nat. Commun. 13 , 4735 (2022)..

Hammes, G. G. Multiple conformational changes in enzyme catalysis. Biochemistry 41 , 8221–8228 (2002)..

Miya shita, A. et al. Synthesis of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP), an atropisomeric chiral bis(triaryl)phosphine, and its use in the rhodium(I)-catalyzed asymmetric hydrogenation of.alpha.-(acylamino)acrylic acids. J. Am. Chem. Soc. 102 , 7932–7934 (1980)..

Chen, Z. et al. Synergetic conformational regulations in ground and excited states for realizing stimulus-responsive and wide-tuning room-temperature phosphorescence. J. Am. Chem. Soc. 145 , 16748–16759 (2023)..

Zhang, Z. Y. et al. Vibration-induced emission (VIE) of N , N’ -disubstituted-dihydribenzo[ a , c ] phenazines: fundamental understanding and emerging applications. Adv. Funct. Mater. 30 , 1902803 (2020)..

Wang, T. et al. Thermally activated and aggregation-regulated excitonic coupling enable emissive high-lying triplet excitons. Angew. Chem. Int. Ed. 61 , e202206681 (2022)..

Liu, Z. J. et al. Direct demonstration of triplet excimer in purely organic room temperature phosphorescence through rational molecular design. Light Sci. Appl. 11 , 142 (2022)..

Wang, J. Q. et al. Management of triplet excitons transition: fine regulation of Förster and dexter energ y transfer simultaneously. Light Sci. Appl. 13 , 35 (2024)..

Li, Q. Q. & Li, Z. Molecular packing: another key point for the performance of organic and polymeric optoelectronic materials. Acc. Chem. Res. 53 , 962–973 (2020)..

Gu, J. Q., Li, Z. & Li, Q. Q. From single molecule to molecular aggregation science. Coord. Chem. Rev. 475 , 214872 (2023)..

Huang, A. R. et al. Organic persistent RTP crystals: from brittle to flexible by tunable self-partitioned molecular packing. Adv. Mater. 35 , 2209166 (2023)..

Fan, Y. Y., Li, Q. Q. & Li, Z. Afterglow bio-applications by utilizing triplet excited states of organic materials. Science China . Chemistry 66 , 2930–2940 (2023)..

Liao, Q. Y., Li, Q. Q. & Li, Z. The key role of molecular packing in luminescence property: from adjacent molecules to molecular aggregates. Adv. Mater. 35 , 2306617 (2023)..

Sun, H. & Zhu, L. L. Achieving purely organic room temperature phosphorescence in aqueous solution. Aggregate 4 , e253 (2023)..

Wei, J. et al. Conformation-dependent dynamic organic phosphorescence through thermal energy driven molecular rotations. Nat. Commun. 14 , 627 (2023)..

Li, S. H. et al. Different molecular conformation and packing determining mechanochromism and room-temperature phosphorescence. Sci. China Mater. 64 , 2813–2823 (2021)..

Zhang, Z. Y. et al. Excited-state conformational/electronic responses of saddle-shaped N , N’ -disubstituted-dihydrodibenzo[ a , c ] phenazines: wide-tuning emission from red to deep blue and white light combination. J. Am. Chem. Soc. 137 , 8509–8520 (2015)..

Zhang, Z. Y. et al. Tuning the conformation and color of conjugated polyheterocyclic skeletons by installing ortho ‐methyl groups. Angew. Chem. Int. Ed. 57 , 9880–9884 (2018)..

Wu, H. W. et al. Crystal multi‐conformational control through deformable carbon‐sulfur bond for singlet‐triplet emissive tuning. Angew. Chem. Int. Ed. 58 , 4328–4333 (2019)..

Zhou, Q., Yang, C. L. & Zhao, Y. L. Dynamic organic room-temperature phosphorescent systems. Chem 9 , 2446–2480 (2023)..

Okazaki, M. et al. Thermally activated delayed fluorescent phenothiazine–dibenzo [ a , j ] phenazine–phenothiazine triads exhibiting tricolor-changing mechanochromic luminescence. Chem. Sci. 8 , 2677–2686 (2017)..

Shi, Y. F. et al. Dynamic B/N lewis pairs: insights into the structural variations and photochromism via light-induced fluorescence to phosphorescence switching. Angew. Chem. Int. Ed. 61 , e202213615 (2022)..

Luo, W. H. et al. Multifunctional fluorescent materials with reversible mechanochromism and distinct photochromism. Adv. Optical Mater. 11 , 2202259 (2023)..

Chai, Z. F. et al. Abnormal room temperature phosphorescence of purely organic boron-containing compounds: the relationship between the emissive behavior and the molecular packing, and the potential related applications. Chem. Sci. 8 , 8336–8344 (2017)..

Yang, Y. Q. et al. Multi-stimulus room temperature phosphorescent polymers sensitive to light and acid cyclically with energy transfer. Angew. Chem. Int. Ed. 62 , e202308848 (2023)..

Gao, Y. et al. Expounding the relationship between molecular conformation and room-temperature phosphorescence property by deviation angle. J. Phys. Chem. Lett. 13 , 3251–3260 (2022)..

Gao, M. X. et al. The effect of molecular conformations and simulated “self-doping” in phenothiazine derivatives on room-temperature phosphorescence. Angew. Chem. Int. Ed. 62 , e202214908 (2023)..

Zhang, G. Q. et al. Polymorphism and reversible mechanochromic luminescence for solid-state difluoroboron avobenzone. J. Am. Chem. Soc. 132 , 2160–2162 (2010)..

Mizuguchi, K., Kageyama, H. & Nakano, H. Mechanochromic luminescence of 4-[bis(4-methylphenyl)amino ] benzaldehyde. Mater. Lett. 65 , 2658–2661 (2011)..

Hariharan, P. S. et al. Self-reversible mechanochromism and thermochromism of a triphenylamine-based molecule: tunable fluorescence and nanofabrication studies. J. Phys. Chem. C. 119 , 9460–9469 (2015)..

Lin, Y. L. et al. Diethylamino functionalized tetraphenylethenes: structural and electronic modulation of photophysical properties, implication for the CIE mechanism and app lication to cell imaging. J. Mater. Chem. C. 3 , 112–120 (2015)..

Zhang, Z. Q. et al. Mechanofluorochromic properties of β-iminoenolate boron complexes tuned by the electronic effects of terminal phenothiazine and phenothiazine- S , S -dioxide. J. Mater. Chem. C. 3 , 4921–4932 (2015)..

Gao, M. X. et al. The same molecule but a different molecular conformation results in a different room temperature phosphorescence in phenothiazine derivatives. J. Mater. Chem. C. 9 , 15375–15380 (2021)..

Xu, Y. W. et al. Recent progress in hot exciton materials for organic light-emitting diodes. Chem. Soc. Rev. 50 , 1030–1069 (2021)..

Wei, Y. C. et al. Overcoming the energy gap law in near-infrared OLEDs by exciton-vibration decoupling. Nat. Photonics 14 , 570–577 (2020)..

Frisch, M. J. et al. Gaussian 09, Rev. D.01 . (Wallingford, CT: Gaussian. Inc, 2009).

Spackman, P. R. et al. CrystalExplorer : a program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystal s. J. Appl. Crystallogr. 54 , 1006–1011 (2021)..

Bu, L. Y. et al. Solid-state fluorescence properties and reversible piezochromic luminescence of aggregation-induced emission-active 9,10-bis[(9,9-dialkylfluorene-2-yl)vinyl ] anthracenes. J. Mater. Chem. C 1 , 2028–2035 (2013)..

Xue, P. C. et al. Reversible mechanochromic luminescence of phenothiazine-based 10,10’-bianthracene derivatives with different lengths of alkyl chains. J. Mater. Chem. C. 3 , 1018–1025 (2015)..

Ito, S. et al. Indolylbenzothiadiazoles with varying substituents on the indole ring: a systematic study on the self-recovering mechanochromic luminescence. RSC Adv. 7 , 16953–16962 (2017)..

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