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Cited by 151Luminescence and Fluorescent MaterialsOrganic Light-Emitting Diodes ResearchPhotochemistry and Electron Transfer Studies

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Thermochromic aggregation-induced dual phosphorescence via temperature-dependent sp3-linked donor-acceptor electronic coupling

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Wang, Tao, Hu, Zhubin, Nie, Xiancheng, Huang, Linkun, Hui, Miao, Sun, Xiang, Zhang, Guoqing·2021·Nature Communications
DOI 10.1038/s41467-021-21676-5PMC PMC7921125

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Abstract

Aggregation-induced emission (AIE) has proven to be a viable strategy to achieve highly efficient room temperature phosphorescence (RTP) in bulk by restricting molecular motions. Here, we show that by utilizing triphenylamine (TPA) as an electronic donor that connects to an acceptor via an sp 3 linker, six TPA-based AIE-active RTP luminophores were obtained. Distinct dual phosphorescence bands emitting from largely localized donor and acceptor triplet emitting states could be recorded at lowered temperatures; at room temperature, only a merged RTP band is present. Theoretical investigations reveal that the two temperature-dependent phosphorescence bands both originate from local/global minima from the lowest triplet excited state (T 1 ). The reported molecular construct serves as an intermediary case between a fully conjugated donor-acceptor system and a donor/acceptor binary mix, which may provide important clues on the design and control of high-freedom molecular systems with complex excited-state dynamics.

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Crossref · 10.1038/s41467-021-21676-5

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Figures

Fig. 1 AIE-active dual-phosphorescence molecular design. a Design concept of AIE-gen donor–sp3 linker–acceptor thermochromic dual phosphorescent dyad via temperature-dependent coupling between two emissive triplet excited states. b Related chemical structures. EWG = electron-withdrawing group.
Fig. 1 AIE-active dual-phosphorescence molecular design. a Design concept of AIE-gen donor–sp3 linker–acceptor thermochromic dual phosphorescent dyad via temperature-dependent coupling between two emissive triplet excited states. b Related chemical structures. EWG = electron-withdrawing group.CC BY · PubMed Central
Fig. 2 AIE investigations. a Normalized absorption spectra (left) of TPA1-5 in optically dilute THF solutions and corresponding hole (blue)–electron (green) distributions (right) calculated based on the TD-DFT method. b Steady-state emission spectra of TPA1-5 in a bicomponent solution mixture showing the AIE process with different THF/water ratios (0–95%, v/v) and related AIE photos under a hand-held UV lamp (water fraction: 0 and 95%, TPA concentration: 2.0 × 10−3 mol/L).
Fig. 2 AIE investigations. a Normalized absorption spectra (left) of TPA1-5 in optically dilute THF solutions and corresponding hole (blue)–electron (green) distributions (right) calculated based on the TD-DFT method. b Steady-state emission spectra of TPA1-5 in a bicomponent solution mixture showing the AIE process with different THF/water ratios (0–95%, v/v) and related AIE photos under a hand-held UV lamp (water fraction: 0 and 95%, TPA concentration: 2.0 × 10−3 mol/L).CC BY · PubMed Central
Fig. 3 Single-crystal XRD analysis. Stick models (top) of TPA1 and TPA3–5 obtained from single-crystal XRD measurements and packing diagrams shown in wireframe model (bottom), indicating no obvious strong π–π intermolecular interactions in the solid state.
Fig. 3 Single-crystal XRD analysis. Stick models (top) of TPA1 and TPA3–5 obtained from single-crystal XRD measurements and packing diagrams shown in wireframe model (bottom), indicating no obvious strong π–π intermolecular interactions in the solid state.CC BY · PubMed Central
Fig. 4 Photophysical investigations for TPA1-5 molecular solids. a Normalized emission spectra of TPA1-5 in air at room temperature (excitation: 365 nm for TPA1, TPA2, and TPA4; 430 nm for TPA3; and 450 nm for TPA5) and corresponding photos showing TPA1-5 excited by 365-nm UV light. b Time-resolved decay profiles of TPA1-5 in air at room temperature (right: fluorescence; left: RTP). c Time-resolved emission spectra of TPA1. d Normalized emission spectra of TPA1 at 77 K. e Normalized phosphorescence emission spectra of TPA1 dissolved in PMMA film (excitation: 375 nm; concentration: 3%, w/w) at different temperatures. f Schematic illustration of the ternary emission process; process 1: fluorescence; process 2: intersystem crossing at 77 and 298 K; process 3: favored intersystem crossing at 298 K; process 4 and 6: phosphorescence; and process 5: thermally activated conformation transformation.
Fig. 4 Photophysical investigations for TPA1-5 molecular solids. a Normalized emission spectra of TPA1-5 in air at room temperature (excitation: 365 nm for TPA1, TPA2, and TPA4; 430 nm for TPA3; and 450 nm for TPA5) and corresponding photos showing TPA1-5 excited by 365-nm UV light. b Time-resolved decay profiles of TPA1-5 in air at room temperature (right: fluorescence; left: RTP). c Time-resolved emission spectra of TPA1. d Normalized emission spectra of TPA1 at 77 K. e Normalized phosphorescence emission spectra of TPA1 dissolved in PMMA film (excitation: 375 nm; concentration: 3%, w/w) at different temperatures. f Schematic illustration of the ternary emission process; process 1: fluorescence; process 2: intersystem crossing at 77 and 298 K; process 3: favored intersystem crossing at 298 K; process 4 and 6: phosphorescence; and process 5: thermally activated conformation transformation.CC BY · PubMed Central
Fig. 5 Temperature-dependent time-resolved emissions of PMMA films for showing dual phosphorescence. Normalized phosphorescence emission spectra of TPA2 (a), TPA3 (b), TPA4 (c), and TPA5 (d) dissolved in PMMA film (Δt = 1 ms; excitation: 375 nm; and concentration: 3%, w/w) at different temperatures showing the two triplet-state emissions.
Fig. 5 Temperature-dependent time-resolved emissions of PMMA films for showing dual phosphorescence. Normalized phosphorescence emission spectra of TPA2 (a), TPA3 (b), TPA4 (c), and TPA5 (d) dissolved in PMMA film (Δt = 1 ms; excitation: 375 nm; and concentration: 3%, w/w) at different temperatures showing the two triplet-state emissions.CC BY · PubMed Central
Fig. 6 Theoretical computations on the conformations and molecular orbital transitions for dual phosphorescence. Calculated relative Gibbs free energies and global/local-minima geometries (T1–1, T1–2, T1–3, and T1–4) of T1 state, the related transition states (TS) between these geometries, the optimal geometries with dihedrals of highlighted atoms, and main molecular orbital transition contributions for T1 emissions (>10%; H HOMO, L LUMO).
Fig. 6 Theoretical computations on the conformations and molecular orbital transitions for dual phosphorescence. Calculated relative Gibbs free energies and global/local-minima geometries (T1–1, T1–2, T1–3, and T1–4) of T1 state, the related transition states (TS) between these geometries, the optimal geometries with dihedrals of highlighted atoms, and main molecular orbital transition contributions for T1 emissions (>10%; H HOMO, L LUMO).CC BY · PubMed Central
Fig. 7 Photophysical properties of TPA6. a Chemical structure of TPA6. b Normalized steady-state and RTP emission (Δt = 3 ms) spectra of TPA6 in air at room temperature; inset: photo showing TPA6 solid excited by 365-nm UV light. c Relative steady-state emission spectra of TPA6 at different temperatures. d Relationship between the emission intensity ratio of 455 and 425 nm (I455/I425) and temperature. e Normalized temperature-dependent phosphorescence emission spectra of TPA6. f Image showing delayed emission (>50 ms) color change at different temperatures.
Fig. 7 Photophysical properties of TPA6. a Chemical structure of TPA6. b Normalized steady-state and RTP emission (Δt = 3 ms) spectra of TPA6 in air at room temperature; inset: photo showing TPA6 solid excited by 365-nm UV light. c Relative steady-state emission spectra of TPA6 at different temperatures. d Relationship between the emission intensity ratio of 455 and 425 nm (I455/I425) and temperature. e Normalized temperature-dependent phosphorescence emission spectra of TPA6. f Image showing delayed emission (>50 ms) color change at different temperatures.CC BY · PubMed Central

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Metadata

Authors
Wang, T., Hu, Z., Nie, X., Huang, L., Hui, M., Sun, X., & Zhang, G.
Affiliations
  • University of Science and Technology of China (CN)
  • New York University Shanghai (CN)
Corresponding author
  • Sun, Xiang
  • Zhang, Guoqing
ORCID
Venue
Nature Communications
Publisher
Springer Science and Business Media LLC
Published
2021-03-01
Volume
12
Issue
1
Pages
1364-1364
ISSN
2041-1723 (ISSN-L)
DOI
10.1038/s41467-021-21676-5
PMC
PMC7921125
OpenAlex
W3135232583
Cited by
151
References
59
Citations by year
2026: 17 · 2025: 19 · 2024: 34 · 2023: 33 · 2022: 32 · 2021: 16
FWCI
8.73
Type
journal article
Language
en
Open access
Licence
Locations
  • Nature Communications (publishedVersion, cc-by)
  • ChemRxiv (acceptedVersion, cc-by-nc-nd)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • RePEc: Research Papers in Economics (submittedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
  • Figshare (submittedVersion, cc-by-nc-nd)
Funders
National Natural Science Foundation of China (21975238)
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
aggregation-induced emission, room-temperature phosphorescence, thermochromism, triphenylamine, triplet state, excited-state dynamics, donor-acceptor systems, molecular aggregation

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