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Science China Chemistry 2024年第7期67卷 2373-2381页

作者： Zhenghao Xia Jingxuan You Haojie An Yirong Wang Jinming Zhang Chunchun Yin Yaohui Cheng Kunfeng Jin Jun Zhang CAS Key Laboratory of Engineering Plastics Institute of ChemistryChinese Academy of Sciences(CAS)Beijing 100190China School of Chemical Sciences University of Chinese Academy of SciencesBeijing 100049China HongDa Research Institute Co. Ltd.Beijing 100176China Key National Laboratory of Solid State Microstructures Collaborative Innovation Center of Advanced MicrostructuresNanjing UniversityNanjing 210023China

We demonstrate a new green solvent consisting of ionic liquid and polyol to achieve a selective fractionation of lignin from biomass.The lignin from corn straw is rich in syringyl unit and phenolic hydroxyl group,resulting in excellent room-temperature phosphorescence(RTP)performance,antioxidation property and long-term photostability.Flexible film,fiber,aerogel and coatings with an ultralong RTP lifetime of 0.654 s are obtained.The lignin from corn straw completely blocks UV light of290–400 nm at an extremely low usage due to many p-coumarate units.When the content is as low as 1.54 mg/g,which is two orders of magnitude lower than the previous reports,the corresponding sunscreen cream has a super-high sun protection factor(SPF)of 183.9.More importantly,the lignin self-assembles into nanospheres of 250–350 nm,preventing penetration into the skin.Such easily-available,abundant,low-cost,safe and natural lignin provides an innovative avenue for sustainable optical function materials.

关键词： lignin phosphorescence anti-ultraviolet biomass ionic liquids

Aggregation-induced barrier to oxygen——a new AIE mechanism for metal clusters with phosphorescence

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National Science Review 2022年第8期9卷 71-79页

作者： Yan Jin Qiu-Chen Peng Si Li Hui-Fang Su Peng Luo Ming Yang Xin Zhang Kai Li Shuang-Quan Zang Ben Zhong Tang Thomas C.W.Mak Henan Key Laboratory of Crystalline Molecular Functional Materials Henan International Joint Laboratory of Tumor Theranostical Cluster MaterialsGreen Catalysis Centerand College of ChemistryZhengzhou University Shenzhen Institute of Aggregate Science and Technology School of Science and EngineeringChinese University of Hong Kong The Hong Kong Branch of the Chinese National Engineering Research Center for Tissue Restoration and Reconstruction Hong Kong University of Science and Technology Department of Chemistry Chinese University of Hong Kong

Metal clusters are useful phosphors, but highly luminescent examples are quite rare. Usually, the phosphorescence of metal clusters is hindered by ambient O2molecules. Transforming this disadvantage into an advantage for meaningful applications of metal clusters presents a formidable challenge. In this work, we used ligand engineering to judiciously prepare colour-tuneable and brightly emitting Cu(I)clusters that are ultrasensitive to O2upon dispersion in a fluid solution or in a solid matrix. When the O2scavenger dimethyl sulfoxide(DMSO) was used as the solvent, joint photo-and oxygen-controlled multicolour switches were achieved for the first time for metal cluster-based photopatterning and photo-anticounterfeiting. More importantly, an aggregation-induced barrier to oxygen, a new aggregation-induced emission mechanism for metal clusters, was proposed, providing a new pathway to realizing the intense emission of metal clusters in the aggregated state. These results are expected to promote the application of metal clusters and enrich the luminescence theory of metal cluster aggregates.

关键词： metal clusters aggregation-induced emission phosphorescence photoresponse O_2 detection

Multiple anti-counterfeiting strategy by integrating up-conversion,down-shifting luminescence, phosphorescence and photochromism into Na YTiO4: Bi/Er phosphors

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Journal of Materials Science & Technology 2022年第35期130卷 219-226页

作者： Yuzhen Wang Xuanyi Yuan Yongge Cao Chaoyang Ma Songshan Lake Materials Laboratory Dongguan 523808China Department of Physics Renmin University of ChinaBeijing 100872China Beijing National Laboratory for Condensed Matter Physics and Institute of Physics Chinese Academy of SciencesBeijing 100190China

With the rapid development of science and technology,the high-security-level anti-counterfeiting technique is essential for ensuring property or information security.In this work,we prepared micron NaYTiO_(4):Bi/Er(NYT:Bi/Er) phosphors with integrating up-conversion(UC) photoluminescence,downshifting(DS) emission,phosphorescence and photochromism(PC) performances for advanced multiple anti-counterfeiting application.Owing to the abundant energy levels of Er^(3+)ions,the UC and DS luminescence behaviors are anticipated.Specifically,the yellow-green emission of Er^(3+)ions can be observed upon 980 nm excitation,and the bright green emission is demonstrated under 281 or 254 nm excitation due to the energy transitions of Er^(3+)ions and the energy transfer process from Bi^(3+)to Er^(3+)ions.Besides,the introduction of Bi^(3+)ions generates defect levels in the matrix and thus leads to phosphorescence.Furthermore,the repeatable PC performance could be triggered by the 365 nm irradiation and vanished with 450 nm illumination or thermal stimulation.To verify the practical usability of NYT:Bi/Er phosphors on anti-counterfeiting applications,some experiments are designed and successfully executed.It is believed that the NYT:Bi/Er phosphors can be a promising candidate for high-security-level multiple anti-counterfeiting.

关键词： Anti-counterfeiting Up-conversion Down shifting phosphorescence Photochromism NaYTiO4 Bi/Er

Sensitized ligand narrow-band phosphorescence for high-efficiency solution-processed OLEDs

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Science China Chemistry 2022年第8期65卷 1559-1568页

作者： Qian Wang Jin-Yun Wang Hao Zeng Li-Yi Zhang Zhong-Ning Chen State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China Fuzhou 350108China University of Chinese Academy of Sciences Beijing 100039China

Narrow-band emission is crucial for high color purity in panel display.Nevertheless,attaining narrow-band emission is highly challenging because either thermally activated delayed fluorescence or phosphorescence in organic and metal-organic compounds originates primarily from multiple charge transfer transitions featured with broad bandwidths.In this work,a general tactic for achieving highly efficient narrow-band emission is proposed by the sensitization of ligand-centered phosphorescence through substantial intermetallic interaction.Relative to weak phosphorescence in mononuclear Pt(Ⅱ)precursors,highly efficient ligand-centered phosphorescence is dramatically activated in Pt(Ⅱ)-Au(Ⅰ)heteronuclear complexes with quantum yield as high as 81%in solutions and 97%in doping films.High-efficiency solution-processed organic light-emitting diodes(OLEDs)with narrow-band emission are successfully attained with external quantum efficiency(EQE)of 21.6%and a full width at half maxima(FWHM)of 36 nm for yellow electroluminescence and EQE of 20.8%and FWHM of 32 nm for green electroluminescence.

关键词： electroluminescence narrow-band emission organic light-emitting diode phosphorescence solution process

Dynamic multi-color long-afterglow and cold-warm white light through phosphorescence resonance energy transfer in host-guest metal-organic frameworks

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Science China Chemistry 2023年第12期66卷 3532-3538页

作者： Shuya Liu Yuhang Lin Dongpeng Yan Beijing Key Laboratory of Energy Conversion and Storage Materials Key Laboratory of RadiopharmaceuticalsMinistry of EducationCollege of ChemistryBeijing Normal UniversityBeijing 100875China

Dynamic tuning of single-color and multi-color(including white-light) luminescence has attracted much attention for applications in various fields;however, effective systems are still scarcity to date. Herein, we report the construction of host-guest metal-organic frameworks(MOFs) serves as an effective strategy to achieve the excitation-and time-dependent long afterglow and white light emitting, simultaneously. The guest-induced structural distortion modulates the single-triplet state intersystem crossing, promotes ligand-to-ligand charge transfer(LLCT) in layer-column MOFs, and further boosts multiple exciton generation of triplet states for multi-color ultralong phosphorescence, as indicated by both experiment and density functional theory(DFT) calculation. By further doping of dyes into MOFs, white-light emitting with tunable color temperature can be facilely obtained, which has been further fabricated into white-light light-emitting diode(LED) with color rendering index of 88.4,higher than that of most as-reported pure inorganics and inorganic-organic hybrid systems. Therefore, this work not only describes a host-guest energy transfer route for dynamic tailoring wide range of color-tunable long-afterglow, but also explores the application prospect of new white-light materials with high color rendering and low blue light for promising display and lighting applications.

关键词： phosphorescence ligand-to-ligand charge transfer white-light metal-organic frameworks long-afterglow

Ultra-long room temperature phosphorescence of indium-based organic inorganic metal halides for naked-eye-visible afterglow

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中国科学:化学英文版 2023年第9期66卷 2576-2582页

作者： Heng Yu Hao Gong Zhaorui Hua Yang Zhang Wenming Sun Shuyan Gong Ganglong Cui Yang Tian Hongbing Fu Beijing Key Laboratory for Optical Materials and Photonic Devices Department of ChemistryCapital Normal UniversityBeijing 100048China Key Laboratory of Theoretical and Computational Photochemistry Ministry of EducationCollege of ChemistryBeijing Normal UniversityBeijing 100875China

Solid-state molecules based on room-temperature phosphorescent(RTP)emission have received extensive attention due to their special optical properties of triplet excitons.However,there are still few solid molecular systems with naked-eye-visible afterglow characteristics.Herein,we introduce 4-phenylbenzylamine(namely PBA)with a long conjugated system into common non-toxic In^(3+)to form an indium-based organic inorganic halide,whose chemical formula is PBA_(3)[InCl_6]·H_(2)O.Interestingly,this hybrid halide generates a RTP emission at 617 nm with a lifetime decay as long as 290.4 ms,expressing a naked-eye-visible afterglow for more than 7 s.The mechanism study shows that the long lifetime RTP originated from the specific lamellar stacking of organic molecules and metal halide units,facilitating the interaction between the inorganic layers and organic layers.Therefore,the material can be potentially used in emergency lighting,information security,and other fields.Meanwhile,this work provides a reference for the design and implementation of a more efficient organic-inorganic hybrid system with the ultralong RTP emission.

关键词： phosphorescence indium 4-phenylbenzylamine halide afterglow

The phosphorescence nanocomposite thin film with rich oxygen vacancy:Towards sensitive oxygen sensor

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Chinese Chemical Letters 2022年第8期33卷 3977-3980页

作者： Jian Yao Jian Kong Lingwei Kong Xinrui Wang Wenying Shi Chao Lu State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical TechnologyBeijing 100029China Key Laboratory of Cosmetic China National Light IndustryBeijing Technology and Business UniversityBeijing 100048China

Organic room temperature phosphorescent(ORTP)materials provide an exciting research direction for phosphorescent oxygen(O_(2)) sensors due to their high sensitivity and rapid response to O_(2).However,most pure ORTP materials are tightly-packed aromatic compound crystals in a face-to-face manner,which largely prohibits effective O_(2) diffusion for sensing.Thus,how to solve this contradiction still faces huge challenges.Here,the use of organic phosphorescent indicator carbon dots(CDs),inorganic matrix layered double hydroxides(LDHs)and polymers(PVA)successfully prepared an ultra-long RTP composite film whose phosphorescence decay intensity is linearly related to O_(2) concentration.More importantly,the use of the abundant O_(2) defects(Vo)on the surface of the inorganic matrix LDHs to adsorb O_(2),which further accelerates the phosphorescence quenching of the thin film and improves the O_(2) response.This strategy will provide the possibility to develop high-sensitivity phosphorescent O_(2) sensors from a new perspective.

关键词： Layered double hydroxides Carbon dots Nanocomposite thin film phosphorescence Oxygen vacancy Oxygen-sensing

Kinetics process of room temperature phosphorescence and fluorescence of gadolinium porphyrin in aqueous solution

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Journal of Rare Earths 2021年第10期39卷 1187-1193,I0001页

作者： Ting Liu Xiyu Zhang Honglin Zhang Hua Zhao Zhiguo Zhang Ye Tian Condensed Matter Science and Technology Institute Harbin Institute of TechnologyHarbin 150001 China School of Materials and Engineering Harbin Institute of TechnologyHarbin 150001China Division of Cardiology The First Affiliated HospitalHarbin Medical UniversityHarbin 150001China

The behavior of room temperature phosphorescence quenching and fluorescence enhancing of gadolinium labeled sinoporphyrin sodium(Gd-DVDMS) in the aqueous solution were studied.Gd-DVDMS was characterized by various techniques including mass spectra,Fourier transform infrared spectra and transmission electron microscopy.The optical behavior was monitored through UV-vis absorption spectra and photoluminescence spectra.The result shows that the phosphorescence intensity gradually quenches,almost disappears after dissolved 120 min,meanwhile the fluorescence intensity enhances 5 times.The above behavior is attributed to the decreased population of Gd-DVDMS as first excited triplet state(T1),Based on the time-invariant of both absorption spectra and phosphorescence decay curves at710 nm of Gd-DVDMS in different dissolution time,the reason for the decreased population of GdDVDMS in T1 state is that the intersystem crossing from first excited state(S1) to T1 is prevented.In addition,the fluorescent decay curves of Gd-DVDMS initially dissolved in the aqueous solution and dissolved for 120 min were also measured for comparison.The big change in fluorescent lifetime further proves the conclusion that intersystem crossing is prevented,meanwhile,the increase in fluorescence intensity is demonstrated.In this work,the possibility of decomposition of Gd-DVDMS is excluded because the phosphorescence decay curve in Gd-DVDMS aqueous solution is sensible to DVDMS.

关键词： Gd-DVDMS phosphorescence Fluorescence Aqueous solution Intersystem crossing Rare earths

Water-induced ultralong room temperature phosphorescence by constructing hydrogen-bonded networks

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Nano Research 2020年第3期13卷 875-881页

作者： Ya-Chuan Liang Yuan Shang Kai-Kai Liu Zhen Liu Wen-Jie Wu Qian Liu Qi Zhao Xue-Ying Wu Lin Dong Chong-Xin Shan Henan Key Laboratory of Diamond Optoelectronic Materials and Devices School of Physics and EngineeringZhengzhou UniversityZhengzhou 450052China Super Computer Center Smart City InstituteZhengzhou UniversityZhengzhou 4500052China The college of Chemistry and Molecular Engineering Zhengzhou UniversityZhengzhou 4500052China

Room temperature phosphorescence(RTP)materials show potential applications in information security and optoelectronic devices,but it is still a challenge to achieve RTP in organic materials under water ambient due to the unstable property of triplet states.Herein,water-induced RTP has been demonstrated in the organic microrod(OMR).Noting that the RTP intensity of the as-prepared OMR is greatly enhanced when water is introduced,and the reason for the enhancement can be attributed to the formation of hydrogen-bonded networks inside the OMR.The hydrogen-bonded networks can confine the molecular motion effectively,leading to the stability of triplet states;thus the lifetime of the OMR can reach 1.64 s after introducing water.By virtue of the long lifetime of the OMR in the presence of water,multilevel data encryption based on the OMR has been demonstrated.

关键词： water-induced phosphorescence triplet states hydrogen-bonded networks

Recent Advances in Purely Organic Room Temperature phosphorescence Polymer

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Chinese Journal of Polymer Science 2019年第4期37卷 383-393,I0006页

作者： Man-Man Fang Jie Yang Zhen Li Institute of Molecular Aggregation Science Tianjin University Department of Chemistry Wuhan University

Room temperature phosphorescence(RTP) has drawn increasing attention for its great potential in practical applications.Polymers with large molecular weights and long chains tend to form coil, which can endow them with a high degree of possible rigidity and result in the much restricted non-radiative transition. Also, the intertwined structure of polymers could isolate the oxygen and humidity effectively, thus reducing the consumption of triplet excitons. In consideration of these points, organic polymers would be another kind of ideal platform to realize RTP effect. This short review summarized the design strategy of the purely organic room temperature phosphorescence polymers, mainly focusing on the building forms of polymers and the corresponding inherent mechanisms,and also gives some outlooks on the further exploration of this field at the end of this paper.

关键词： Room temperature phosphorescence Polymers Non-radiative transition