共查询到20条相似文献,搜索用时 15 毫秒
1.
Dr. Jan Lorkowski Dylan Bouetard Patrick Yorkgitis Dr. Milan Gembicky Dr. Thierry Roisnel Dr. Nicolas Vanthuyne Prof. Dr. Dominik Munz Dr. Ludovic Favereau Prof. Dr. Guy Bertrand Dr. Marc Mauduit Dr. Rodolphe Jazzar 《Angewandte Chemie (International ed. in English)》2023,62(33):e202305404
Organic circularly polarized luminescence (CPL)-active molecular emitters featuring dynamic propeller-like luminophores were prepared in one step from cyclic(alkyl)(amino) carbenes (CAACs). These molecules exhibit through-space arene-arene π-delocalization and rapid intramolecular inter-system crossing (ISC) in line with their helical character. 相似文献
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Angshuman Das Saikat Ghosh Prof. Dr. Subi J. George 《Angewandte Chemie (International ed. in English)》2023,62(38):e202308281
Efficient circularly polarized luminescence (CPL) from purely organic molecules holds great promise for applications in displays, sensing, and bioimaging. However, achieving high dissymmetry values (glum) from organic chromophores remains a significant challenge. Herein, we present a bioinspired approach using adenosine triphosphate (ATP)-triggered supramolecular polymerization of a naphthalene diimide-derived monomer ( ANSG ) to induce CPL with a remarkable glum value of 1.1×10−2. The ANSG molecules undergo a templated, chiral self-assembly through a cooperative growth mechanism in the presence of ATP, resulting in scrolled nanotubes with aggregation-induced enhanced emission (AIEE) and induced CPL. Furthermore, we demonstrate the concept of chiroptical amplification of induced CPL by efficiently amplifying asymmetry using a mixture of chiral ATP and achiral pyrophosphate. This innovative approach opens numerous opportunities in the emerging field of circularly polarized luminescence. 相似文献
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Dr. Pengfei Wu Prof. Dr. Adriana Pietropaolo Dr. Mariagrazia Fortino Dr. Masayoshi Bando Prof. Dr. Katsuhiro Maeda Dr. Tatsuya Nishimura Shuhei Shimoda Dr. Hiroyasu Sato Prof. Dr. Naofumi Naga Prof. Dr. Tamaki Nakano 《Angewandte Chemie (International ed. in English)》2023,62(29):e202305747
Optically active, hyperbranched, poly(fluorene-2,4,7-triylethene-1,2-diyl) [poly(fluorenevinylene)] derivatives bearing a neomenthyl group and a pentyl group at the 9-position of the fluorene backbone at various ratios acted as a chirality donor (host polymers) efficiently included naphthalene, anthracene, pyrene, 9-phenylanthracene, and 9,10-diphenyanthracene as a chirality acceptor (guest molecules) in their interior space in film as well as in solution, with the guest molecules exhibiting intense circular dichroism through chirality transfer with chirality amplification. The efficiency of the chirality transfer was much higher with higher-molar-mass polymers than lower-molar-mass ones as well as with hyperbranched polymers compared to the analogous linear ones. The hyperbranched polymers include the small molecules in their complex structure without any specific interactions at various stoichiometries. The included molecules may have ordered intermolecular arrangement that may be somewhat similar to those of liquid crystals. Naphthalene, anthracene, and pyrene included in the polymer exhibited efficient circularly polarized luminescence, where the chirality was remarkably amplified in excited states, and anthracene exhibited especially high anisotropies in the emission on the order of 10−2. 相似文献
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Dr. Xihao Tang Xiangji Liao Xinting Cai Jialin Wu Xueying Wu Qianni Zhang Yilun Yan Prof. Shengrun Zheng Prof. Huawei Jiang Prof. Jun Fan Prof. Songliang Cai Prof. Weiguang Zhang Dr. Yi Liu 《Angewandte Chemie (International ed. in English)》2023,62(4):e202216310
Despite significant progress on the design and synthesis of covalent organic frameworks (COFs), precise control over microstructures of such materials remains challenging. Herein, two chiral COFs with well-defined one-handed double-helical nanofibrous morphologies were constructed via an unprecedented template-free method, capitalizing on the diastereoselective formation of aminal linkages. Detailed time-dependent experiments reveal the spontaneous transformation of initial rod-like aggregates into the double-helical microstructures. We have further demonstrated that the helical chirality and circular dichroism signal can be facilely inversed by simply adjusting the amount of acetic acid during synthesis. Moreover, by transferring chirality to achiral fluorescent molecular adsorbents, the helical COF nanostructures can effectively induce circularly polarized luminescence with the highest luminescent asymmetric factor (glum) up to ≈0.01. 相似文献
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Yuncong Xue Can Zhang Tongjin Lv Prof. Dr. Longzhen Qiu Prof. Dr. Feng Wang 《Angewandte Chemie (International ed. in English)》2023,62(18):e202300972
Circularly polarized photodetectors require chiral light absorption materials with high sensing efficiency and low costs. Here readily accessible point chirality has been introduced to dicyanostilbenes as the chiral source, facilitating remote chirality transfer to the π-aromatic core by cooperative supramolecular polymerization. The single-handed supramolecular polymers display powerful circularly polarized photodetection capability with a dissymmetry factor value as high as 0.83, superior to those of π-conjugated small molecules and oligomers. Strong chiral amplification occurs between the enantiopure sergeants and the achiral soldiers. The resulting supramolecular copolymers exhibit comparable photodetection efficiency to those of the homopolymeric ones, with a 90 % decrease in the enantiopure compound consumption. Therefore, cooperative supramolecular polymerization provides an effective yet economical avenue toward circularly polarized photodetection applications. 相似文献
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Adi Azoulay Sapir Shekef Aloni Prof. Lidan Xing Ayelet Tashakory Prof. Yitzhak Mastai Prof. Menny Shalom 《Angewandte Chemie (International ed. in English)》2023,62(40):e202311389
The facile synthesis of chiral materials is of paramount importance for various applications. Supramolecular preorganization of monomers for thermal polymerization has been proven as an effective tool to synthesize carbon and carbon nitride-based (CN) materials with ordered morphology and controlled properties. However, the transfer of an intrinsic chemical property, such as chirality from supramolecular assemblies to the final material after thermal condensation, was not shown. Here, we report the large-scale synthesis of chiral CN materials capable of enantioselective recognition. To achieve this, we designed supramolecular assemblies with a chiral center that remains intact at elevated temperatures. The optimized chiral CN demonstrates an enantiomeric preference of ca. 14 %; CN electrodes were also prepared and show stereoselective interactions with enantiomeric probes in electrochemical measurements. By adding chirality to the properties transferrable from monomers to the final product of a thermal polymerization, this study confirms the potential of using supramolecular precursors to produce carbon and CN materials and electrodes with designed chemical properties. 相似文献
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Oliver G. Willis Dr. Francesco Zinna Prof. Lorenzo Di Bari 《Angewandte Chemie (International ed. in English)》2023,62(25):e202302358
In recent years, circularly polarized luminescence (CPL) has witnessed a renaissance, due to the increased popularity of CPL as a spectroscopic technique and greater accessibility to instrumentation. New efficient CPL emitters have been designed and many applications, ranging from electronic devices to microscopy have been proposed. Most examples of CPL are within the visible range, while few cases of near infrared (NIR) CPL active complexes are available. NIR-CPL compounds may have applications in the telecommunication industry, electronic devices and bioassays. In the following, we shall give an overview of the recent developments allowing for the measurements of NIR-CPL, and describe the chiroptical properties of metal complexes which achieve this feat. 相似文献
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Dr. Moulali Vaddamanu Dr. Arruri Sathyanarayana Yamane Masaya Shohei Sugiyama Ozaki Kazuhisa Dr. Kavitha Velappan Muneshwar Nandeshwar Dr. Kyohei Hisano Osamu Tsutsumi Prof. Dr. Ganesan Prabusankar 《化学:亚洲杂志》2021,16(5):521-529
The synthesis and the luminescence features of three gold(I)-N-heterocyclic carbene (NHC) complexes are presented to study how the n-alkyl group can influence the luminescence properties in the crystalline state. The mononuclear gold(I)-NHC complexes, [( L1 )Au(Cl)] ( 1 ), [( L2 )Au(Cl)] ( 2 ), and [( L3 )Au(Cl)] ( 3 ) were isolated from the reactions between [(tht)AuCl] and corresponding NHC ligand precursors, [N-(9-acridinyl)-N’-(n-butyl)-imidazolium chloride, ( L1 .HCl)], [N-(9-acridinyl)-N’-(n-pentyl)-imidazolium chloride, ( L2 .HCl)] and [N-(9-acridinyl)-N’-(n-hexyl)-imidazolium chloride, ( L3 .HCl)]. Their single-crystal X-ray analysis reveals the influence of the n-alkyl groups on solid-state packing. A comparison of the luminescence features of 1 – 3 with n-alkyl substituents is explored. The molecules 1 – 3 depicted blue emission in the solution state, while the yellow emission (for 1 ), greenish-yellow emission (for 2 ), and blue emission (for 3 ) in the crystalline phase. This paradigm emission shift arises from n-butyl to n-pentyl and n-hexyl in the crystalline state due to the carbon-carbon rotation of the n-alkyl group, which tends to promote unusual solid packing. Hence n-alkyl group adds a novel emission property in the crystalline state. Density Functional Theory and Time-Dependent Density Functional Theory calculations were carried out for monomeric complex, N-(9-acridinyl)-N’-(n-heptyl)imidazole-2-ylidene gold(I) chloride and dimeric complex, N-(9-acridinyl)-N’-(n-heptyl)imidazole-2-ylidene gold(I) chloride to understand the structural and electronic properties. 相似文献
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Dr. Xun-Hui Xu Dr. Shu-Ming Kang Run-Tan Gao Dr. Zheng Chen Prof. Dr. Na Liu Prof. Dr. Zong-Quan Wu 《Angewandte Chemie (International ed. in English)》2023,62(20):e202300882
Developing high performance and environment-friendly fluoropolymers is greatly desired. In this work, we found that 2-diazo-1,1,1-trifluoroethane can be polymerized by air-stable alkyne-palladium(II) catalysts following a living polymerization mechanism, affording a fluoropolymer, poly(trifluoromethyl methylene) in high yield with controlled molar mass and low dispersity. This polymer bears trifluoromethyl on every main chain atom and thus has good resistance to chemical corrosion, high hydrophobicity, and excellent dielectric constant with low dielectric loss. Due to the steric hindrance between the trifluoromethyl pendants, the synthetic poly(trifluoromethyl methylene) can twist into a stable helix. The one-handed preferred helices synthesized using chiral PdII-catalysts exhibit high optical activity and circularly polarized luminescence. Remarkably, such polymer can be completely degraded to (E)-1,1,1,4,4,4-hexafluorobut-2-ene at high temperatures (>280 °C). Additionally, taking advantage of the living chain end, the polymer can be further modified. 相似文献
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Jia-Hui Chen Zhi-Yu Jiang Prof. Dr. Hai Xiao Prof. Dr. Shuo Tong Dr. Tan-Hao Shi Prof. Dr. Jieping Zhu Prof. Dr. Mei-Xiang Wang 《Angewandte Chemie (International ed. in English)》2023,62(15):e202301782
Herein we report a two-directional cyclization strategy for the synthesis of highly strained depth-expanded oxygen-doped chiral molecular belts of the zigzag-type. From the easily accessible resorcin[4]arenes, an unprecedented cyclization cascade generating fused 2,3-dihydro-1H-phenalenes has been developed to access expanded molecular belts. Stitching up the fjords through intramolecular nucleophilic aromatic substitution and ring-closing olefin metathesis reactions furnished a highly strained O-doped C2-symmetric belt. The enantiomers of the acquired compounds exhibited excellent chiroptical properties. The calculated parallelly aligned electric ( μ ) and magnetic ( m ) transition dipole moments are translated to the high dissymmetry factor (|glum| up to 0.022). This study provides not only an appealing and useful strategy for the synthesis of strained molecular belts but also a new paradigm for the fabrication of belt-derived chiroptical materials with high CPL activities. 相似文献
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Olimpia Mamula Alex von Zelewsky Thomas Bark Grald Bernardinelli 《Angewandte Chemie (International ed. in English)》1999,38(19):2945-2948
Its information content is infinitely smaller than that of DNA, but its structure (see picture) ressembles the double-stranded helix produced by nature. This self-assembled, configurationally predetermined coordination polymer is built up from enantiopure chiral bipyridine-type ligands and silver ions. 相似文献
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Dr. Yi Qin Qing-Hui Ling Yu-Te Wang Dr. Yi-Xiong Hu Prof. Lianrui Hu Prof. Xiaoli Zhao Prof. Dong Wang Prof. Hai-Bo Yang Prof. Lin Xu Prof. Ben Zhong Tang 《Angewandte Chemie (International ed. in English)》2023,62(36):e202308210
A series of covalent organic cages built from fluorophores capable of aggregation-induced emission (AIE) were elegantly prepared through the reduction of preorganized M2(LA)3(LB)2-type metallacages, simultaneously taking advantage of the synthetic accessibility and well-defined shapes and sizes of metallacages, the good chemical stability of the covalent cages as well as the bright emission of AIE fluorophores. Moreover, the covalent cages could be further post-synthetically modified into an amide-functionalized cage with a higher quantum yield. Furthermore, these presented covalent cages proved to be good energy donors and were used to construct light-harvesting systems employing Nile Red as an energy acceptor. These light-harvesting systems displayed efficient energy transfer and relatively high antenna effect, which enabled their use as efficient photocatalysts for a dehalogenation reaction. This research provides a new avenue for the development of luminescent covalent cages for light-harvesting and photocatalysis. 相似文献
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Sha Wang Linhong Long Xiaoyu Zhang Liang Ling Prof. Dr. Hui Chen Prof. Dr. Xiaoming Zeng 《Angewandte Chemie (International ed. in English)》2023,62(44):e202312856
Geminal cross couplings using multiple components enable the formation of several different bonds at one site in the building of tertiary and quaternary alkanes. Nevertheless, there are remaining issues of concern—cleavage of two geminal bonds and control of selectivity present challenges. We report here the geminal cross couplings of three components by reactions of dihaloalkanes with organomagnesium and chlorosilanes or alkyl tosylates by Cr catalysis, affording the formation of geminal C−C/C−Si or C−C/C−C bonds in the creation of tertiary and quaternary alkanes. The geminal couplings are catalyzed by low-cost CrCl2, enabling the sluggishness of competitive Kumada-type side couplings and homocouplings of Grignard reagents, in achieving high chemoselectivity. Experimental and theoretical studies indicate that two geminal C-halide bonds are continuously cleaved by Cr to afford a metal carbene intermediate, which couples with a Grignard reagent, followed by silylation, in the formation of geminal C−C and C−Si bonds via a novel inner-sphere radical coupling mechanism. These three-component geminal cross couplings are value-addition to the synthesis of commercial drugs and bioactive molecules in medicinal chemistry. 相似文献
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Jin-Ping Si Wen-Jing Wang Jun Chang Kun-Lin Huang Zhi-Hui Zhang Sheng-Chun Chen Ming-Yang He Qun Chen 《无机化学与普通化学杂志》2020,646(21):1739-1747
Reactions of the aromatase inhibitor letrozole derivative 4,4'-(1H-1,2,4-triazol-1-yl)methylene-bis(benzonic acid) (H2tzmb) with ZnII, CdII, or PbII salts under similar conditions resulted in the generation of three coordination polymers, namely, {[Zn(tzmb)(H2tzmb)] · H2O}n ( 1 ), [Cd(tzmb)(H2O)2]n ( 2 ), and {[Pb(tzmb)(H2O)] · DMF}n ( 3 ), respectively. Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, and thermogravimetric analyses. Complex 1 features a twofold 2D → 2D interpenetrated network based on corrugated 63- hcb layers, and complex 2 exhibits a flat 2D 4.82- fes network, whereas complex 3 presents a 3D hex net based on infinite rod-shaped secondary building units. The remarkable structural diversity may illustrate the powerful effect of metal ions on coordination assemblies. The spectroscopic, thermal, and photoluminescent properties of complexes 1 – 3 were investigated. In addition, the catalytic activity of 1 in the solvent-free ring-opening polymerization of ε-caprolactone was also discussed. 相似文献
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