Efficient and long-lived room-temperature organic phosphorescence: theoretical descriptors for molecular designs
Abstract
Room-temperature phosphorescence (RTP) with long afterglow from pure organic materials has attracted great attention for its potential applications in biological imaging, digital encryption, optoelectronic devices, and so on. Organic materials have been long considered to be nonphosphorescent owing to their weak molecular spin–orbit coupling and high sensitivity to temperature. However, recently, some purely organic compounds have demonstrated highly efficient RTP with long afterglow upon aggregation, while others fail. Namely, it remains a challenge to expound on the underlying mechanisms. In this study, we present the molecular descriptors to characterize the phosphorescence efficiency and lifetime. For a prototypical RTP system consisting of a carbonyl group and π-conjugated segments, the excited states can be regarded as an admixture of n → π* (with portion α) and π → π* (portion β). Starting from the phosphorescent process and El-Sayed rule, we deduced that (i) the intersystem crossing (ISC) rate of S 1 → T n is mostly governed by the modification of the product of α and β and (ii) the ISC rate of T 1 → S 0 is determined by the β value of T 1 . Thus, the descriptors (γ = α × β, β) can be employed to describe the RTP character of organic molecules. From hybrid quantum mechanics and molecular mechanics (QM/MM) calculations, we illustrated the relationships among the descriptors (γ, β), phosphorescence efficiency and lifetime, and spin–orbit coupling constants. We stressed that the large γ and β values are favorable for the strong and long-lived RTP in organic materials. Experiments have reported confirmations of these molecular design rules.
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“This is because a rigid external environment may effectively inhibit the non-radiative relaxation at its triplet excited state [14], and the environment’s oxygen barrier efficiency/ability may also inhibit the triplet-triplet energy transfer process between the phosphors and the triplet oxygen to reduce the non-radiat…”
Background
- Authors
- Ma, H., Peng, Q., An, Z., Huang, W., & Shuai, Z.
- Affiliations
- Nanjing Tech University (CN)
- Chinese Academy of Sciences (CN)
- Tsinghua University (CN)
- Corresponding author
- Shuai, Zhigang
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2018-12-19
- Volume
- 141
- Issue
- 2
- Pages
- 1010-1015
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2905046851
- Cited by
- 613
- References
- 42
- Citations by year
- 2026: 50 · 2025: 83 · 2024: 103 · 2023: 77 · 2022: 95 · 2021: 96 · 2020: 62 · 2019: 47
- FWCI
- 19.15
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Ministry of Science and Technology of the People's Republic of China (2017YFA0204501, 2015CB655002)
- Nanjing Tech University (3983500201)
- National Natural Science Foundation of China (21788102, 91622121, 21473214)
- Chinese Academy of Sciences (XDB12020200)
- Topics
- Physical Sciences › Materials Science › Materials Chemistry › Luminescence and Fluorescent Materials
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Organic Light-Emitting Diodes Research
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Keywords
- room-temperature phosphorescence, persistent luminescence, organic phosphors, molecular descriptors, spin-orbit coupling, intersystem crossing, phosphorescence efficiency, phosphorescence lifetime, aggregation-induced emission, QM/MM calculations, molecular design rules
- MeSH terms
- Density Functional Theory, Models, Chemical, Organic Chemicals, Temperature, Luminescence
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