A highly efficient open-shell singlet luminescent diradical with strong magnetoluminescence properties

Alim Abdurahman; Li Shen; Jingmin Wang; Meiling Niu; Ping Li; Qiming Peng; Jianpu Wang; Geyu Lu

doi:10.1038/s41377-023-01314-z

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A highly efficient open-shell singlet luminescent diradical with strong magnetoluminescence properties

Original Articles

- A highly efficient open-shell singlet luminescent diradical with strong magnetoluminescence properties
- Light: Science & Applications Vol. 12, Issue 12, Pages: 2636-2643(2023)
- Affiliations：
  
  1.State Key Laboratory of Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, Qianjin Avenue 2699, Changchun 130012, China
  2.College of Chemical Engineering and Environmental Chemistry, Weifang University, Weifang 261061, China
  3.Key Laboratory of Flexible Electronics (KLOFE), Institute of Advanced Materials (IAM) & School of Flexible Electronics (Future Technologies), Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, China
  4.Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM) National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China
- Author bio：
  
  Alim Abdurahman (alim@jlu.edu.cn)
  Qiming Peng (iamqmpeng@njtech.edu.cn)
  Geyu Lu (Lugy@jlu.edu.cn)
- Funds：
- DOI：10.1038/s41377-023-01314-z
  CLC：
- Published：31 December 2023，
  
  Published Online：14 November 2023，
  
  Received：17 July 2023，
  
  Revised：14 October 2023，
  
  Accepted：23 October 2023
- Accepted：
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Abdurahman, A. et al. A highly efficient open-shell singlet luminescent diradical with strong magnetoluminescence properties. Light: Science & Applications, 12, 2636-2643 (2023).
DOI：

Abdurahman, A. et al. A highly efficient open-shell singlet luminescent diradical with strong magnetoluminescence properties. Light: Science & Applications, 12, 2636-2643 (2023). DOI： 10.1038/s41377-023-01314-z.

摘要

Abstract

Developing open-shell singlet (OS) diradicals with high luminescent properties and exceptional single-molecule magnetoluminescence (ML) performance is extremely challenging. Herein

we propose a concept to enhance luminescent efficiency by adjusting the donor conjugation of OS diradicals

thereby achieving a highly luminescent diradical

DR1

with outstanding stability and making it a viable option for use in the emitting layer of organic light-emitting diodes (OLEDs). More importantly

the 0.5 wt%-DR1 doped film demonstrates significant single-molecule magnetoluminescence (ML) properties. A giant ML value of 210% is achieved at a magnetic field of 7 T

showing the great potential of DR1 in magneto-optoelectronic devices.

关键词

Keywords

references

Wu, J. S.Diradicaloids. (New York: Jenny Stanford Publishing, 2022).

Sun, Z. et al. Low band gap polycyclic hydrocarbons: from closed-shell near infrared dyes and semiconductors to open-shell radicals.Chem. Soc. Rev.41, 7857–7889 (2012)..

Zeng, Z. B. et al. Pro-aromatic and anti-aromatic π-conjugated molecules: an irresistible wish to be diradicals.Chem. Soc. Rev.44, 6578–6596 (2015)..

Abe, M. Diradicals.Chem. Rev.113, 7011–7088 (2013)..

Ratera, I.&Veciana, J. Playing with organic radicals as building blocks for functional molecular materials.Chem. Soc. Rev.41, 303–349 (2012)..

Stuyver, T. et al. Do diradicals behave like radicals?Chem. Rev.119, 11291–11351 (2019)..

Dressler, J. J.&Haley, M. M. Learning how to fine‐tune diradical properties by structure refinement.J. Phys. Org. Chem.33, e4114 (2020)..

Rajca, A. Organic diradicals and polyradicals: from spin coupling to magnetism?Chem. Rev.94, 871–893 (1994)..

Casado, J.Para-quinodimethanes: a unified review of the quinoidal-versus-aromatic competition and its implications.Top. Curr. Chem.375, 73 (2017)..

Sun, Z., Zeng, Z. B.&Wu, J. S. Zethrenes, extendedp-quinodimethanes, and periacenes with a singlet biradical groundstate.Acc. Chem. Res.47, 2582–2591 (2014)..

Kubo, T. Closed-shell and open-shell dual nature of singlet diradical compounds.Pure Appl. Chem.95, 363–375 (2023)..

Gopalakrishna et al. From open-shell singlet diradicaloids to polyradicaloids.Chem. Commun.54, 2186–2199 (2018)..

Feng,Z. et al. Recent advances in stable main group element radicals: preparation and characterization.Chem. Soc. Rev.51, 5930–5973 (2022)..

Hu, X. G. et al. The electronic applications of stable diradicaloids: present and future.J. Mater. Chem. C6, 11232–11242 (2018)..

Chen, Z. X., Li, Y.&Huang, F. Persistent and stable organic radicals: design.Synth. Appl. Chem.7, 288–332 (2021)..

Konishi, A.&Kubo, T. Benzenoid quinodimethanes.Top. Curr. Chem.375, 83 (2017)..

Gallagher, N. M., Olankitwanit, A.&Rajca, A. High-spin organic molecules.J. Org. Chem.80, 1291–1298 (2015)..

Hinkel, F., Freudenberg, J.&Bunz, U. H. F. A stable π‐conjugated singlet biradical.Angew. Chem. Int. Ed.55, 9830–9832 (2016)..

Rudebusch, G. E. et al. Diindeno-fusion of an anthracene as a design strategy for stable organic biradicals.Nat. Chem.8, 753–759 (2016)..

Dressler, J. J. et al. Thiophene and its sulfur inhibit indenoindenodibenzothiophene diradicals from low-energy lying thermal triplets.Nat. Chem.10, 1134–1140 (2018)..

Li, L. et al. Highly conducting single-molecule topological insulators based on mono-and di-radical cations.Nat. Chem.14, 1061–1067 (2022)..

Zeng, Z. B. et al. Push–pull type oligo (N-annulated perylene) quinodimethanes: chain length and solvent-dependent ground states and physical properties.J. Am. Chem. Soc.137, 8572–8583 (2015)..

Arikawa, S., Shimizu, A.&Shintani, R. Azoniadibenzo [a,j]phenalenide: a polycyclic zwitterion with singlet biradical character.Angew. Chem.131, 6481–6485 (2019)..

Xu, X. S. et al. 6,6′-Biindeno[1,2-b]anthracene: an open-shell biaryl with high diradical character.J. Am. Chem. Soc.145, 3891–3896 (2023)..

Xu, T. T. et al. Antiaromatic dicyclopenta[b,g]/[a,f]naphthalene isomers showing an open-shell singlet ground state with tunable diradical character.J. Am. Chem. Soc.143, 20562–20568 (2021)..

Konishi, A. et al. Synthesis and characterization of dibenzo[a,f]pentalene: harmonization of the antiaromatic and singlet biradical character.J. Am. Chem. Soc.139, 15284–15287 (2017)..

Barker, J. E. et al. Molecule isomerism modulates the diradical properties of stable singlet diradicaloids.J. Am. Chem. Soc.142, 1548–1555 (2020)..

Jousselin-Oba, T. et al. Excellent semiconductors based on tetracenotetracene and pentacenopentacene: From stable closed-shell to singlet open-shell.J. Am. Chem. Soc.141, 9373–9381 (2019)..

Li, Y. et al. Kinetically blocked stable heptazethrene and octazethrene: closed-shell or open-shell in the ground state?J. Am. Chem. Soc.134, 14913–14922 (2012)..

Su, Y. T. et al. Tuning ground states of bis(triarylamine) dications: from a closed‐shell singlet to a diradicaloid with an excited triplet state.Angew. Chem.126, 2901–2905 (2014)..

Guo, J. X. et al. Boron-containing organic diradicaloids: dynamically modulating singlet diradical character by lewis acid–base coordination.J. Am. Chem. Soc.143, 18272–18279 (2021)..

Koide, T. et al. A stable non-kekulé singlet biradicaloid frommeso-free 5,10,20,25-tetrakis(pentafluorophenyl)-substituted [26]hexaphyrin(1.1.1.1.1.1).J. Am. Chem. Soc.132, 7246–7247 (2010)..

Kamada, K. et al. Singlet diradical character from experiment.J. Phys. Chem. Lett.1, 937–940 (2010)..

Fu, X. Y. et al. A polycyclic aromatic hydrocarbon diradical with pH-responsive magnetic properties.Chem. Sci.11, 5565–5571 (2020)..

Liu, J. Z. et al. Tetrabenzo[a,f,j,o]perylene: a polycyclic aromatic hydrocarbon with an open‐shell singlet biradical ground state.Angew. Chem.127, 12619–12623 (2015)..

Zhang, S. Y. et al. High-spin (S=1) blatter-based diradical with robust stability and electrical conductivity.J. Am. Chem. Soc.144, 6059–6070 (2022)..

Lambert, C. Towards polycyclic aromatic hydrocarbons with a singlet open‐shell ground state.Angew. Chem. Int. Ed.50, 1756–1758 (2011)..

Su, Y. T. et al. Thermally controlling the singlet–triplet energy gap of a diradical in thesolid state.Chem. Sci.7, 6514–6518 (2016)..

Wang, Q. et al. Cyclopenta ring fused bisanthene and its charged species with open‐shell singlet diradical character and global aromaticity/anti‐aromaticity.Angew. Chem. Int. Ed.56, 11415–11419 (2017)..

Han, Y. et al. Bisazapentalene dication: global aromaticity and open-shell singlet ground state.Org. Lett.25, 3380–3385 (2023)..

Namai, H. et al. Thermoluminescence and a new organic light-emitting diode (OLED) based on triplet− triplet fluorescence of the trimethylenemethane (TMM) biradical.J. Am. Chem. Soc.129, 9032–9036 (2007)..

Hattori, Y. et al. Luminescent Mono‐, Di‐, and triradicals: bridging polychlorinated triarylmethyl radicals by triarylamines and triarylboranes.Chemistry25, 15463–15471 (2019)..

Feng, Z. T. et al. A stable triplet diradical emitter.Chem. Sci.12, 15151–15156 (2021)..

Arikawa, S. et al. A kinetically stabilized nitrogen‐Doped triangulene cation: stable and NIR fluorescent diradical cation with triplet ground state.Angew. Chem. Int. Ed.62, e202302714 (2023)..

Abdurahman, A. et al. A highly stable organic luminescent diradical.Angew. Chem. Int. Ed.62, e202300772 (2023)..

Kimura, S. et al. Magnetoluminescence in a photostable, brightly luminescent organic radical in a rigid environment.Angew. Chem.130, 12893–12897 (2018)..

Kimura, S. et al. Radical-based coordination polymers as a platform for magnetoluminescence.J. Am. Chem. Soc.143, 5610–5615 (2021)..

Kimura, S. et al. A ground-state-dominated magnetic field effect on the luminescence of stable organic radicals.Chem. Sci.12, 2025–2029 (2021)..

Kimura, S. et al. Excimer emission and magnetoluminescence of radical-based zinc(Ⅱ) complexes doped in host crystals.Chem. Commun.56, 11195–11198 (2020)..

Matsuoka, R. et al. Single-molecule magnetoluminescence from a spatially confined persistent diradical emitter.J. Am. Chem. Soc.145, 13615–13622 (2023)..

Desroches, M. et al. Breaking bonds and forming nanographene diradicals with pressure.Angew. Chem.129, 16430–16435 (2017)..

Bleaney, B.&Bowers, K. D. Anomalous paramagnetism of copper acetate.Proc. R. Soc. A214, 451–465 (1952)..

Armet, O. et al. Inert carbon free radicals. 8. Polychlorotriphenylmethyl radicals: synthesis, structure, and spin-density distribution.J. Phys. Chem.91, 5608–5616 (1987)..

Peng, Q. M. et al. Organic light‐emitting diodes using a neutral π radical as emitter: the emission from a doublet.Angew. Chem.127, 7197–7201 (2015)..

Gamero, V. et al. [4-(N-Carbazolyl)-2,6-dichlorophenyl]bis(2,4,6-trichlorophenyl)methyl radical an efficient red light-emitting paramagnetic molecule.Tetrahedron Lett.47, 2305–2309 (2006)..

Abdurahman, A. et al. Understanding the luminescent nature of organic radicals for efficient doublet emitters and pure-red light-emitting diodes.Nat. Mater.19, 1224–1229 (2020)..

Lu, C. et al. Towards efficient and stable donor‐acceptor luminescent radicals.Adv. Mater.35, 2208190 (2023)..

Li, P. et al. Constructing stable phenalenyl-based neutral radicals: a theoretical study.J. Mater. Chem. C8, 12224–12230 (2020)..

Miao, Y. F. et al. Microcavity top-emission perovskite light-emitting diodes.Light9, 89 (2020)..

Hu, B., Yan, L.&Shao, M. Magnetic‐field effects in organic semiconducting materials and devices.Adv. Mater.21, 1500–1516 (2009)..

He, L. et al. Magnetophotoluminescence line-shape narrowing through interactions between excited states in organic semiconducting materials.Phys. Rev. B89, 155304 (2014)..

Xu, J. et al. Tailoring spin mixtures by ion-enhanced Maxwell magnetic coupling in color-tunable organic electroluminescent devices.Light7, 46–57 (2018)..

Wang, J. P. et al. Control of exciton spin statistics through spin polarization in organic optoelectronic devices.Nat. Commun.3, 1191 (2012)..

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