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| 3. |
- Wu, Hongwei, et al.
(författare)
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Crystal Multi-Conformational Control Through Deformable Carbon-Sulfur Bond for Singlet-Triplet Emissive Tuning
- 2019
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Ingår i: Angewandte Chemie International Edition. - : WILEY-V C H VERLAG GMBH. - 1433-7851 .- 1521-3773. ; 58:13, s. 4328-4333
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Tidskriftsartikel (refereegranskat)abstract
- Crystal-state luminophores have been of great interest in optoelectronics for years, whereas the excited state regulation at the crystal level is still restricted by the lack of control ways. We report that the singlet-triplet emissive property can be profoundly regulated by crystal conformational distortions. Employing fluoro-substituted tetrakis(arylthio)benzene luminophores as prototype, we found that couples of molecular conformations formed during different crystallizations. The deformable carbon-sulphur bond essentially drove the distortion of the molecular conformation and varied the stacking mode, together with diverse non-covalent interactions, leading to the proportional adjustment of the fluorescence and phosphorescence bands. This intrinsic strategy was further applied for solid-state multicolor emissive conversion and mechanoluminescence, probably offering new insights for design of smart crystal luminescent materials.
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| 4. |
- Wu, Hongwei, et al.
(författare)
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Multidimensional Structure Conformation of Persulfurated Benzene for Highly Efficient Phosphorescence
- 2021
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Ingår i: ACS Applied Materials and Interfaces. - : AMER CHEMICAL SOC. - 1944-8244 .- 1944-8252. ; 13:1, s. 1314-1322
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Tidskriftsartikel (refereegranskat)abstract
- It is a challenge to acquire, realize, and comprehend highly emissive phosphorescent molecules. Herein, we report that, using persulfurated benzene compounds as models, phosphorescence can be strongly enhanced through the modification of molecular conformation and crystal growth conditions. By varying the peripheral groups in these compounds, we were able to control their molecular conformation and crystal growth mode, leading to one- (1D), two- (2D), and three-dimensional (3D) crystal morphologies. Two kinds of typical molecular conformations were separately obtained in these crystals through substituent group control or the solvent effect. Importantly, a symmetrical 3,3-conformer exhibits that a planar central benzene ring prefers a 3D-type crystal growth mode, demonstrating high phosphorescence efficiency. Such outcome is attributed to the strong crystal protection effect of the 3D crystal and the bright global minimum (GM) boat-like T-1 state of the symmetrical 3,3-conformer. The conformation studies further reveal small deformation of the inner benzene ring in both singlet and triplet states. The GM boat-like T-1 state is indicated by theoretical calculations, which is far away from the conical intersection (CI) point between the S-0 and T-1 potential energy surfaces. Meanwhile, the small energy gap between S-1 and T-1 states and the considerable spin-orbit coupling matrix elements allow an efficient population of the T-1 state. Combined with the crystal protection and conformation effect, the 3,3- conformer crystal shows high phosphorescence efficiency. The unsymmetrical 2,4-conformer conformation with the twisted central benzene ring leads to 1D or 2D crystal growth mode, which has a weak crystal protection effect. In addition, the unsymmetrical conformation has a dark GM T-1 state that is very close to the T-1-S-0 CI point, implying an efficient nonradiative T-1-S-0 quenching. Thus, weak phosphorescence was observed from the unsymmetrical conformation. This study provides an insight for the development of highly emissive phosphorescent materials.
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| 5. |
- Gao, Lei, et al.
(författare)
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Hydrophilic Cocrystals with Water Switched Luminescence
- 2024
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Ingår i: Angewandte Chemie International Edition. - : WILEY-V C H VERLAG GMBH. - 1433-7851 .- 1521-3773.
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Tidskriftsartikel (refereegranskat)abstract
- Utilizing water molecules to regulate the luminescence properties of solid materials is highly challenging. Herein, we develop a strategy to produce water-triggered luminescence-switching cocrystals by coassembling hydrophilic donors with electron-deficient acceptors, where 1,2,4,5-Tetracyanobenzene (TCNB) was used as the electron acceptor and pyridyl benzimidazole derivatives were used as the electron donors enabling multiple hydrogen-bonds. Two cocrystals, namely 2PYTC and 4PYTC were obtained and showed heat-activated emission, and such emission could be quenched or weakened by adding water molecules. The cocrystal structure exhibited the donor molecule that can form multiple hydro bonds with water and acceptor molecules due to the many nitrogen atoms of them. The analyses of the photophysical data, powder X-ray diffraction, and other data confirmed the reversible fluorescence "on-off" effects were caused by eliminating and adding water molecules in the crystal lattice. The density functional theory calculations indicate that the vibration of the O-H bond of water molecules in the cocrystal can absorb the excitation energy and suppress fluorescence. Furthermore, the obtained cocrystals also showed temperature, humidity, and H+/NH4+ responsive emission behavior, which allows their applications as thermal and humidity sensors, and multiple information encryptions. This research paves the way for preparing intelligent hydrophilic organic cocrystal luminescent materials. Hydrophilic donors with electron-deficient acceptors were coassembled to achieve luminescence-switching cocrystals triggered by water molecules. The obtained cocrystals show a strong water absorption ability and excellent fluorescence properties. The emission of cocrystals can be reversibly switched by heating and water. Finally, the obtained cocrystals show potential applications in temperature-humidity and acid-base responses.+image
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| 6. |
- Li, Yiran, et al.
(författare)
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Photoinduced Radical Emission in a Coassembly System
- 2021
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Ingår i: Angewandte Chemie International Edition. - : John Wiley & Sons. - 1433-7851 .- 1521-3773. ; 60:44, s. 23842-23848
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Tidskriftsartikel (refereegranskat)abstract
- Developing radical emission at ambient conditions is a challenging task since radical species are unstable in air. In the present work, we overcome this challenge by coassembling a series of tricarbonyl-substituted benzene molecules with polyvinyl alcohol (PVA). The strong hydrogen bonds between the guest dopants and the PVA host matrix protect the free radicals of carbonyl compounds after light irradiation, leading to strong solid state free radical emission. Changing temperature and peripheral functional groups of the tricarbonyl-substituted benzenes can influence the intensity of the radical emission. Quantum-chemical calculations predict that such free radical fluorescence originates from anti-Kasha D-2 -> D-0 vertical emission by the anion radicals. The photoinduced radical emission by the tricarbonyl-substituted benzenes was successfully utilized for information encryption application.
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| 7. |
- Li, Yiran, et al.
(författare)
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Vibration-Regulated Multi-State Long-Lived Emission from Star-Shaped Molecules
- 2022
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Ingår i: Angewandte Chemie International Edition. - : WILEY-V C H VERLAG GMBH. - 1433-7851 .- 1521-3773. ; 61:48
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Tidskriftsartikel (refereegranskat)abstract
- How to utilize molecular vibration to tune triplet-involved emissions in multiple states is highly challenging. Here, star-shaped triphenylamine derivatives have been employed as model systems to understand how molecular vibration affects thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) emissions in multiple states. Nonplanar, star-shaped conformations allow molecules to generate appropriate vibrations in the solution state, facilitating vibronic coupling between their T-1 and T-2 states to generate effective TADF. More importantly, a relatively dispersed state can allow the molecules to efficiently vibrate in the solid state, and a crystalline environment further promotes a more efficient TADF. Lastly, by suppressing molecular vibration to inhibit the TADF, ultra-long RTP was observed upon doping these molecules into polymers. These molecules can be used in information encryption and storage as well as bioimaging.
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| 8. |
- Liu, Juanjuan, et al.
(författare)
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Photoinduced Carbonyl Radical Luminescence in Host-Guest Systems
- 2023
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Ingår i: ACS Applied Materials and Interfaces. - : AMER CHEMICAL SOC. - 1944-8244 .- 1944-8252. ; 15:50, s. 58888-58896
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Tidskriftsartikel (refereegranskat)abstract
- Developing a free radical emission system in different states, especially in water, is highly challenging and desired. Herein, a host-guest coassembly strategy was used to protect the in situ photoactivated radical emission of carbonyl compounds in solid and aqueous solutions by doping them into a series of small molecules with hydroxyl groups. The intermolecular interactions between host and guest and the electron-donating ability of the hydroxyl group can significantly promote the formation and stabilization of luminescence by carbonyl radicals. Accordingly, the stimuli-responsive property of the free radical system was investigated in detail, and the self-assembled aggregates showed photoactive and thermoresponsive behaviors. In addition, an advanced ammonia compound identification system can be built based on a radical emission system. Our design strategy sheds light on developing free radical systems that can emit in various states, which will greatly broaden the application range of free radicals.
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| 9. |
- Tong, Danqing, et al.
(författare)
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Achieving short-wavelength free radical emission by combining small conjugated structure and anti-Kasha emission
- 2023
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Ingår i: Dyes and pigments. - : ELSEVIER SCI LTD. - 0143-7208 .- 1873-3743. ; 219
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Tidskriftsartikel (refereegranskat)abstract
- Since the natural narrow bandgaps of free radicals usually lead to emission in the long-wavelength region, it is still of great challenge to design radical luminescent materials with stable and short-wavelength emission in the ambient environment. In this work, a series of dicarbonyl-substituted organic molecules with small conjugated structures were used to form free radicals with short-wavelength radical emission. These low-conjugated mol-ecules with only one benzene ring showed stable photoinduced free radical emission after doping with poly-methyl methacrylate (PMMA) because the rigid polymer environment could help stabilize the free radicals and limit the non-radiative energy transfer. Moreover, PMMA with electron-withdrawing groups could promote the generation of carbonyl radical cations. The theoretical calculation suggests that the free radical with anti-Kasha emission derived from high energy excited state (D4 or D5) would directly relax to the ground state, combining with the small spin delocalization of the low conjugation free radical, leading to short-wavelength emission. More importantly, such free radical emissions could also respond to external stimulation such as light irradiation or heat treatment. These materials show great potential in lithography information recording and information encryption. This design strategy provides new insights into molecular and functional diversity of free radical materials.
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| 10. |
- Wu, Hongwei, et al.
(författare)
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Tuning for Visible Fluorescence and Near-Infrared Phosphorescence on a Unimolecular Mechanically Sensitive Platform via Adjustable CH-pi Interaction
- 2017
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 9:4, s. 3865-3872
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Tidskriftsartikel (refereegranskat)abstract
- CH-pi interaction-assisted alignment of organic conjugated systems has played an important role to regulate molecular electronic and photophysical properties, whereas harnessing such a smart noncovalent interaction into the tuning of unimolecular complex emissive bands covering a wide spectral region remains a challenging research topic. Since the tuning for visible and near-infrared emissive properties in a single pi-functional platform relates to its multicolor luminescent behaviors and potential superior application in analysis, bioimaging, and sensing, herein, we report a proportional control of the singlet and triplet emissions that cover visible and near-infrared spectral regions, respectively, can be straightforwardly achieved by CH-pi interaction-assisted self-assembly at the unimolecular level. Employing an octathionaphthalene-based single luminophore as a prototype, we find that a strength-adjustable CH-pi interaction-assisted self-assembly can be established in mixed DMF/H2O and in the film state. The hybridization of planar local excited and intramolecular charge transfer transitions occurs on the basis, allowing a competitive inhibition to the intersystem crossing process to generate a complex emission composed of visible fluorescence and near-infrared phosphorescence. Furthermore, reversible mechanochromic and mechanoluminescent conversions of the corresponding solid sample can both be observed to rely on a corresponding self-assembly alternation. These results can probably provide new visions for the development of future intelligent and multifunctional luminescent materials.
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