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1.
Ting Zhang Xiang Ma Hongwei Wu Liangliang Zhu Yanli Zhao He Tian 《Angewandte Chemie (International ed. in English)》2020,59(28):11206-11216
Materials displaying room‐temperature phosphorescence (RTP) have been attracting wide attention in recent years due to their distinctive characteristics including long emissive lifetime and large Stokes shift, and their various applications. Most synthesized RTP materials are metal complexes that display enhanced intersystem crossing and crystallization is a common way to restrict nonradiative transition. Amorphous metal‐free RTP materials, which do not rely on expensive and toxic metals and can be prepared in a straightforward fashion, have become an important branch of the field. This Minireview summarizes recent progress in amorphous RTP materials according to the approaches used to immobilize phosphors: host–guest interactions, molecule doping, copolymers, and small‐molecule self‐assembly. Some existing challenges and insightful perspectives are given at the end of the Minireview, which should benefit the future design and development of amorphous metal‐free RTP materials. 相似文献
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Yunxiang Lei Wenbo Dai Jianxin Guan Shuai Guo Fei Ren Yudai Zhou Prof. Jianbing Shi Prof. Bin Tong Prof. Zhengxu Cai Prof. Junrong Zheng Prof. Yuping Dong 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16188-16194
Organic materials with long-lived, color-tunable phosphorescence are potentially useful for optical recording, anti-counterfeiting, and bioimaging. Herein, we develop a series of novel host–guest organic phosphors allowing dynamic color tuning from the cyan (502 nm) to orange red (608 nm). Guest materials are employed to tune the phosphorescent color, while the host materials interact with the guest to activate the phosphorescence emission. These organic phosphors have an ultra-long lifetime of 0.7 s and a maximum phosphorescence efficiency of 18.2 %. Although color-tunable inks have already been developed using visible dyes, solution-processed security inks that are temperature dependent and display time-resolved printed images are unprecedented. This strategy can provide a crucial step towards the next-generation of security technologies for information handling. 相似文献
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Room-temperature phosphorescence (RTP) materials with high efficiency have attracted much attention because they have unique characteristics that cannot be realized in conventional fluorescent materials. Unfortunately, efficient RTP in metal-free organic materials is very rare and it has traditionally been considered as the feature to divide purely organic compounds from organometallic and inorganic compounds. There has been increasing research interest in the design and preparation of metal-free organic RTP materials in recent years. It has been reported that intermolecular interactions make a big difference to the photophysical behavior of organic molecules. In this regard, herein, the parameters that affect RTP efficiency are discussed, and a brief review of recent intermolecular halogen-/hydrogen-bonding strategies for efficient RTP in metal-free organic materials are provided. The opportunities and challenges are finally elaborated in the hope of guiding promising directions for the design and application of RTP materials. 相似文献
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Taking advantages of the impressing behaviors of room-temperature phosphorescence (RTP), the explorations in RTP materials are not only limited to efficient emission and ultralong lifetime of phosphorescence. The discovery and creation of stimuli-responsive properties have become the major pursuit, which will lay a solid foundation for future applications in RTP materials. Based on this, a review centered on recent progress of stimuli-responsive RTP materials is summarized to show frontier development in polymer systems. Different kinds of stimuli-responsive factors including light, oxygen, temperature, mechanical force and pH regulations are investigated in this review. Many potential applications and promising strategies are deeply discussed with the hope to assist future studies in this area. 相似文献
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Dr. Zhi-Yuan Zhang Wen-Wen Xu Wen-Shi Xu Jie Niu Xiao-Han Sun Prof. Dr. Yu Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18907-18913
An enhancement strategy is realized for ultralong bright room-temperature phosphorescence (RTP), involving polymerization between phosphor monomers and acrylamide and host–guest complexation interaction between phosphors and cucurbit[6,7,8]urils (CB[6,7,8]). The non-phosphorescent monomers exhibit 2.46 s ultralong lifetime after copolymerizing with acrylamide. The improvement is due to the rich hydrogen bond and carbonyl within the polymers which promote intersystem crossing, suppress nonradiative relaxation and shield quenchers effectively. By tuning the ratio of chromophores, a series of phosphorescent copolymers with different lifetimes and quantum yields are prepared. The complexation of macrocyclic hosts CB[6,7,8] promote the RTP of polymers by blocking aggregation-caused quenching, and offsetting the losses of aforementioned interaction provided by polymer. Multiple lifetime-encoding for digit and character encryption are achieved by utilizing the difference of their lifetimes. 相似文献
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Tailoring Intermolecular Interactions for Efficient Room‐Temperature Phosphorescence from Purely Organic Materials in Amorphous Polymer Matrices 下载免费PDF全文
Sungbaek Seo Jaehun Jung Prof. Dr. Jinsang Kim 《Angewandte Chemie (International ed. in English)》2014,53(42):11177-11181
Herein we report a rational design strategy for tailoring intermolecular interactions to enhance room‐temperature phosphorescence from purely organic materials in amorphous matrices at ambient conditions. The built‐in strong halogen and hydrogen bonding between the newly developed phosphor G1 and the poly(vinyl alcohol) (PVA) matrix efficiently suppresses vibrational dissipation and thus enables bright room‐temperature phosphorescence (RTP) with quantum yields reaching 24 %. Furthermore, we found that modulation of the strength of halogen and hydrogen bonding in the G1–PVA system by water molecules produced unique reversible phosphorescence‐to‐fluorescence switching behavior. This unique system can be utilized as a ratiometric water sensor. 相似文献
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Dr. Kohei Takahashi Shunsuke Shimo Dr. Emanuel Hupf Junichi Ochiai Christina A. Braun Dr. William Torres Delgado Letian Xu Prof. Dr. Gang He Prof. Dr. Eric Rivard Prof. Dr. Nobuharu Iwasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8479-8483
Guest-controlled diastereoselective self-assembly of a diboryltellurophene and a chiral tetrol bearing an indacene backbone was achieved to give either hetero- or homochiral macrocyclic boronic esters, selectively. The heterochiral isomer (hetero-[2+2]Te) exhibited a higher inclusion ability for electron-deficient aromatic guests, leading to effective quenching of phosphorescence from the diboryltellurophene moieties. The reported macrocycles collectively represent a promising arene sensing approach based on phosphorescence. 相似文献
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Prof. Hisahiro Sasabe Prof. Yuki Kato Dr. Yuichiro Watanabe Tatsuya Ohsawa Dr. Naoya Aizawa Prof. Wataru Fujiwara Dr. Yong-Jin Pu Prof. Hiroshi Katagiri Prof. Junji Kido 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(71):16294-16300
Exploration of pure metal-free organic molecules that exhibit strong room-temperature phosphorescence (RTP) is an emerging research topic. In this regard, unveiling the design principles for an efficient RTP molecule is an essential, but challenging, task. A small molecule is an ideal platform to precisely understand the fundamental role of each functional component because the parent molecule can be easily derivatized. Here, the RTP behaviors of a series of 3-pyridylcarbazole derivatives are presented. Experimental studies in combination with theoretical calculations reveal the crucial role of the n orbital on the central pyridine ring in the dramatic enhancement of the intersystem crossing between the charge-transfer-excited singlet state and the locally excited triplet states. Single-crystal X-ray crystallographic studies apparently indicate that both the pyridine ring and fluorine atom contribute to the enhancement of the RTP because of the restricted motion owing to weak C−H⋅⋅⋅N and H⋅⋅⋅F hydrogen-bonding interactions. The single crystal of the fluorine-substituted derivative shows an ultra-long phosphorescent lifetime (τP) of 1.1 s and a phosphorescence quantum yield (ΦP) of 1.2 %, whereas the bromine-substituted derivative exhibits τP of 0.15 s with a ΦP of 7.9 %. We believe that this work provides a fundamental and universal guideline for the generation of pure organic molecules exhibiting strong RTP. 相似文献
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Dr. Nans Roques Anthony Tovar-Molle Dr. Carine Duhayon Dr. Stéphane Brandès Alex Spieß Prof. Dr. Christoph Janiak Dr. Jean-Pascal Sutter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(61):e202201935
Five isostructural microporous supramolecular architectures prepared by H-bonded assembly between the hexa-anionic complex [Zr2(Ox)7]6− (Ox=oxalate, (C2O4)2−) and tripodal cations (H3-TripCH2-R)3+ with R=H, CH3, OH and OBn (Bn=CH2Ph) are reported. The possibility to obtain the same structure using a mixture of tripodal cations with different R group (R=OH and R=CH3) has also been successfully explored, providing a unique example of three-component H-bonded porous framework. The resulting SPA-1(R) materials feature 1D pores decorated by R groups, with apparent pore diameters ranging from 3.0 to 8.5 Å. Influence of R groups on the sorption properties of these materials is evidenced through CO2 and H2O vapor sorption/desorption experiments, as well as with I2 capture/release experiments in liquid media. This study is one of the first to demonstrate the possibility of tuning the porosity and exerting precise control over the chemical functionalization of the pores in a given H-bonded structure, without modifying the topology of the reference structure, and thus finely adjusting the sorption characteristics of the material. 相似文献
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Yating Chen Yufeng Xie Hao Shen Dr. Yunxiang Lei Dr. Yunbing Zhou Wenbo Dai Prof. Zhengxu Cai Miaochang Liu Prof. Xiaobo Huang Prof. Huayue Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(72):17376-17380
Dual/multi-component organic doped systems with room-temperature phosphorescence (RTP) properties have been developed. However, the unknown luminescence mechanism still greatly limits the development of the doped materials. Herein, a new doped system exhibiting phosphorescence/fluorescence dual emission (Φphos=4–24 % and τphos=101–343 ms) is successfully constructed through prediction and design. A series of isoquinoline derivatives with different alkoxy chains were selected as the guests. Benzophenone was chosen as the host owing to the characteristics of low melting point and good crystallinity. The alkoxy chain lengths of the guests are first reported to be used to control the fluorescence and phosphorescence intensities of the doped materials, which results in different prompt emission colors. Additionally, the doped ratio of the guest and host can also control the luminous intensities of the materials. In particular, the doped materials still exhibit phosphorescent properties even if the ratio of the guest/host is as low as 1:100 000. 相似文献
11.
Amorphous Pure Organic Polymers for Heavy‐Atom‐Free Efficient Room‐Temperature Phosphorescence Emission 下载免费PDF全文
Prof. Xiang Ma Chao Xu Jie Wang Prof. He Tian 《Angewandte Chemie (International ed. in English)》2018,57(34):10854-10858
Pure organic, heavy‐atom‐free room‐temperature phosphorescence (RTP) materials have attracted much attention and have potential applications in photoelectric and biochemical material fields owing to their rich excited state properties. They offer long luminescent lifetime, diversified design, and facile preparation. However, recent achievements of efficient phosphorescence under ambient conditions mainly focus on ordered crystal lattices or embedding into rigid matrices, which require strict growth conditions and have poor reproducibility. Herein, we developed a concise approach to give RTP with a decent quantum yield and ultralong phosphorescence lifetime in the amorphous state by radical binary copolymerization of acrylamide and different phosphors with oxygen‐containing functional groups. The cross‐linked hydrogen‐bonding networks between the polymeric chains immobilize phosphors to suppress non‐radiative transitions and provide a microenvironment to shield quenchers. 相似文献
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Back Cover: Tailoring Intermolecular Interactions for Efficient Room‐Temperature Phosphorescence from Purely Organic Materials in Amorphous Polymer Matrices (Angew. Chem. Int. Ed. 42/2014) 下载免费PDF全文
Sungbaek Seo Jaehun Jung Prof. Dr. Jinsang Kim 《Angewandte Chemie (International ed. in English)》2014,53(42):11382-11382
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Dr. Yuki Ohishi Kentaro Masuda Kazuki Kudo Prof. Dr. Hajime Abe Prof. Dr. Masahiko Inouye 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):785-793
Generally, cage-shaped hosts for saccharides can bind strongly to guest molecules because of the three-dimensional preorganized hydrogen-bonding sites. However, the preparation of cage molecules is often difficult because of the low yield of the macrocyclization step. Here, we report a three-arm-shaped molecule possessing pyridine-acetylene-phenol units as a new kind of host having a preorganized three-dimensional hydrogen-bonding site. This three-arm-shaped host was readily prepared compared to a cage-shaped analogue. This host associated with lipophilic glycosides to form chiral complexes, and the association constants were sufficiently high as to be comparable to those of the cage-shaped analogue. Furthermore, this host extracted native monosaccharides into a lipophilic solvent. 相似文献
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Wei Wang Prof. Dr. Shuo Tong Prof. Dr. Qi-Qiang Wang Prof. Dr. Yu-Fei Ao Prof. Dr. De-Xian Wang Prof. Dr. Jieping Zhu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(65):e202202507
The small Stokes shift and weak emission in the solid state are two main shortcomings associated with the boron-dipyrromethene (BODIPY) family of dyes. This study presents the design, synthesis and luminescent properties of boron difluoro complexes of 2-aryl-5-alkylamino-4-alkylaminocarbonylthiazoles. These dyes display Stokes shifts (Δλ, 77–101 nm) with quantum yields (ϕFL) up to 64.9 and 34.7 % in toluene solution and in solid state, respectively. Some of these compounds exhibit dual fluorescence and room-temperature phosphorescence (RTP) emission properties with modulable phosphorescence quantum yields (ϕPL) and lifetime (τp up to 251 μs). The presence of intramolecular H-bonds and negligible π-π stacking revealed by X-ray crystal structure might account for the observed large Stokes shift and significant solid-state emission of these fluorophores, while the enhanced spin-orbit coupling (SOC) of iodine and the self-assembly driven by halogen bonding, π-π and C−H…π interactions could be responsible for the observed RTP of iodine containing phosphors. 相似文献
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Yunxiang Lei Wenbo Dai Jianxin Guan Shuai Guo Fei Ren Yudai Zhou Jianbing Shi Bin Tong Zhengxu Cai Junrong Zheng Yuping Dong 《Angewandte Chemie (International ed. in English)》2020,59(37):16054-16060
Organic materials with long‐lived, color‐tunable phosphorescence are potentially useful for optical recording, anti‐counterfeiting, and bioimaging. Herein, we develop a series of novel host–guest organic phosphors allowing dynamic color tuning from the cyan (502 nm) to orange red (608 nm). Guest materials are employed to tune the phosphorescent color, while the host materials interact with the guest to activate the phosphorescence emission. These organic phosphors have an ultra‐long lifetime of 0.7 s and a maximum phosphorescence efficiency of 18.2 %. Although color‐tunable inks have already been developed using visible dyes, solution‐processed security inks that are temperature dependent and display time‐resolved printed images are unprecedented. This strategy can provide a crucial step towards the next‐generation of security technologies for information handling. 相似文献