High stability and luminescence efficiency in donor–acceptor neutral radicals not following the Aufbau principle

Haoqing Guo; Qiming Peng; Xian Kai Chen; Qinying Gu; Shengzhi Dong; Emrys W. Evans; Alexander J. Gillett; Xin Ai; Ming Zhang; Dan Credgington; Veaceslav Coropceanu; Richard H. Friend; Jean Luc Brédas; Feng Li

doi:10.1038/s41563-019-0433-1

High stability and luminescence efficiency in donor–acceptor neutral radicals not following the Aufbau principle

Haoqing Guo, Qiming Peng, Xian Kai Chen, Qinying Gu, Shengzhi Dong, Emrys W. Evans, Alexander J. Gillett, Xin Ai, Ming Zhang, Dan Credgington, Veaceslav Coropceanu, Richard H. Friend, Jean Luc Brédas, Feng Li

Research output: Contribution to journal › Article › peer-review

121 Citations (Scopus)

Abstract

With their unusual electronic structures, organic radical molecules display luminescence properties potentially relevant to lighting applications; yet, their luminescence quantum yield and stability lag behind those of other organic emitters. Here, we designed donor–acceptor neutral radicals based on an electron-poor perchlorotriphenylmethyl or tris(2,4,6-trichlorophenyl)methyl radical moiety combined with different electron-rich groups. Experimental and quantum-chemical studies demonstrate that the molecules do not follow the Aufbau principle: the singly occupied molecular orbital is found to lie below the highest (doubly) occupied molecular orbital. These donor–acceptor radicals have a strong emission yield (up to 54%) and high photostability, with estimated half-lives reaching up to several months under pulsed ultraviolet laser irradiation. Organic light-emitting diodes based on such a radical emitter show deep-red/near-infrared emission with a maximal external quantum efficiency of 5.3%. Our results provide a simple molecular-design strategy for stable, highly luminescent radicals with non-Aufbau electronic structures.

Original language	English
Pages (from-to)	977-984
Number of pages	8
Journal	Nature Materials
Volume	18
Issue number	9
DOIs	https://doi.org/10.1038/s41563-019-0433-1
Publication status	Published - Sept 1 2019
Externally published	Yes

All Science Journal Classification (ASJC) codes

Chemistry(all)
Materials Science(all)
Condensed Matter Physics
Mechanics of Materials
Mechanical Engineering

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10.1038/s41563-019-0433-1

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Guo, H., Peng, Q., Chen, X. K., Gu, Q., Dong, S., Evans, E. W., Gillett, A. J., Ai, X., Zhang, M., Credgington, D., Coropceanu, V., Friend, R. H., Brédas, J. L., & Li, F. (2019). High stability and luminescence efficiency in donor–acceptor neutral radicals not following the Aufbau principle. Nature Materials, 18(9), 977-984. https://doi.org/10.1038/s41563-019-0433-1

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title = "High stability and luminescence efficiency in donor–acceptor neutral radicals not following the Aufbau principle",

abstract = "With their unusual electronic structures, organic radical molecules display luminescence properties potentially relevant to lighting applications; yet, their luminescence quantum yield and stability lag behind those of other organic emitters. Here, we designed donor–acceptor neutral radicals based on an electron-poor perchlorotriphenylmethyl or tris(2,4,6-trichlorophenyl)methyl radical moiety combined with different electron-rich groups. Experimental and quantum-chemical studies demonstrate that the molecules do not follow the Aufbau principle: the singly occupied molecular orbital is found to lie below the highest (doubly) occupied molecular orbital. These donor–acceptor radicals have a strong emission yield (up to 54%) and high photostability, with estimated half-lives reaching up to several months under pulsed ultraviolet laser irradiation. Organic light-emitting diodes based on such a radical emitter show deep-red/near-infrared emission with a maximal external quantum efficiency of 5.3%. Our results provide a simple molecular-design strategy for stable, highly luminescent radicals with non-Aufbau electronic structures.",

author = "Haoqing Guo and Qiming Peng and Chen, {Xian Kai} and Qinying Gu and Shengzhi Dong and Evans, {Emrys W.} and Gillett, {Alexander J.} and Xin Ai and Ming Zhang and Dan Credgington and Veaceslav Coropceanu and Friend, {Richard H.} and Br{\'e}das, {Jean Luc} and Feng Li",

note = "Funding Information: H.G., Q.P., S.D., X.A., M.Z. and F.L. are grateful for financial support from the National Natural Science Foundation of China (grant nos. 91833304, 51673080 and 11804156), the National Key R&D Programme of China (grant no. 2016YFB0401001), the National Key Basic Research and Development Programme of China (973 programme, grant no. 2015CB655003) and the programme {\textquoteleft}JLUSTIRT{\textquoteright} (grant no. 2019TD-33). Q.P. Funding Information: acknowledges support from the Nanjing Tech Start-up Grant (38274017104). X.-K.C., V.C. and J.-L.B. acknowledge support from the Georgia Institute of Technology, Georgia Research Alliance, Vasser-Woolley Foundation and Kyulux. Q.G., D.C., E.W.E., A.J.G. and R.H.F. would like to thank the EPSRC for funding this work (EP/M01083X/1, EP/ M005143/1). Q.G. is also grateful for financial support from the China Scholarship Council and Cambridge Trust. D.C. also acknowledges support from the Royal Society (grant no. UF130278). F.L. is an academic visitor at the Cavendish Laboratory, Cambridge, and is supported by the Talents Cultivation Programme (Jilin University, China). Publisher Copyright: {\textcopyright} 2019, The Author(s), under exclusive licence to Springer Nature Limited.",

year = "2019",

month = sep,

day = "1",

doi = "10.1038/s41563-019-0433-1",

language = "English",

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pages = "977--984",

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T1 - High stability and luminescence efficiency in donor–acceptor neutral radicals not following the Aufbau principle

AU - Guo, Haoqing

AU - Peng, Qiming

AU - Chen, Xian Kai

AU - Gu, Qinying

AU - Dong, Shengzhi

AU - Evans, Emrys W.

AU - Gillett, Alexander J.

AU - Ai, Xin

AU - Zhang, Ming

AU - Credgington, Dan

AU - Coropceanu, Veaceslav

AU - Friend, Richard H.

AU - Brédas, Jean Luc

AU - Li, Feng

N1 - Funding Information: H.G., Q.P., S.D., X.A., M.Z. and F.L. are grateful for financial support from the National Natural Science Foundation of China (grant nos. 91833304, 51673080 and 11804156), the National Key R&D Programme of China (grant no. 2016YFB0401001), the National Key Basic Research and Development Programme of China (973 programme, grant no. 2015CB655003) and the programme ‘JLUSTIRT’ (grant no. 2019TD-33). Q.P. Funding Information: acknowledges support from the Nanjing Tech Start-up Grant (38274017104). X.-K.C., V.C. and J.-L.B. acknowledge support from the Georgia Institute of Technology, Georgia Research Alliance, Vasser-Woolley Foundation and Kyulux. Q.G., D.C., E.W.E., A.J.G. and R.H.F. would like to thank the EPSRC for funding this work (EP/M01083X/1, EP/ M005143/1). Q.G. is also grateful for financial support from the China Scholarship Council and Cambridge Trust. D.C. also acknowledges support from the Royal Society (grant no. UF130278). F.L. is an academic visitor at the Cavendish Laboratory, Cambridge, and is supported by the Talents Cultivation Programme (Jilin University, China). Publisher Copyright: © 2019, The Author(s), under exclusive licence to Springer Nature Limited.

PY - 2019/9/1

Y1 - 2019/9/1

N2 - With their unusual electronic structures, organic radical molecules display luminescence properties potentially relevant to lighting applications; yet, their luminescence quantum yield and stability lag behind those of other organic emitters. Here, we designed donor–acceptor neutral radicals based on an electron-poor perchlorotriphenylmethyl or tris(2,4,6-trichlorophenyl)methyl radical moiety combined with different electron-rich groups. Experimental and quantum-chemical studies demonstrate that the molecules do not follow the Aufbau principle: the singly occupied molecular orbital is found to lie below the highest (doubly) occupied molecular orbital. These donor–acceptor radicals have a strong emission yield (up to 54%) and high photostability, with estimated half-lives reaching up to several months under pulsed ultraviolet laser irradiation. Organic light-emitting diodes based on such a radical emitter show deep-red/near-infrared emission with a maximal external quantum efficiency of 5.3%. Our results provide a simple molecular-design strategy for stable, highly luminescent radicals with non-Aufbau electronic structures.

AB - With their unusual electronic structures, organic radical molecules display luminescence properties potentially relevant to lighting applications; yet, their luminescence quantum yield and stability lag behind those of other organic emitters. Here, we designed donor–acceptor neutral radicals based on an electron-poor perchlorotriphenylmethyl or tris(2,4,6-trichlorophenyl)methyl radical moiety combined with different electron-rich groups. Experimental and quantum-chemical studies demonstrate that the molecules do not follow the Aufbau principle: the singly occupied molecular orbital is found to lie below the highest (doubly) occupied molecular orbital. These donor–acceptor radicals have a strong emission yield (up to 54%) and high photostability, with estimated half-lives reaching up to several months under pulsed ultraviolet laser irradiation. Organic light-emitting diodes based on such a radical emitter show deep-red/near-infrared emission with a maximal external quantum efficiency of 5.3%. Our results provide a simple molecular-design strategy for stable, highly luminescent radicals with non-Aufbau electronic structures.

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JO - Nature Materials

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ER -

High stability and luminescence efficiency in donor–acceptor neutral radicals not following the Aufbau principle

Abstract

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