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Understanding AIE and ACQ phenomenon of organometallic iridium(Ⅲ) complexes by simple cationization engineering

Chinese Chemical Letters 2024年第2期35卷 553-557页

作者： Weilin Song Huiting Mao Ying Gao Yaxuan Yao Guo-Gang Shan Zhongmin Su State Key laboratory of Supramolecular Structure and Materials Institute of Theoretical ChemistryCollege of ChemistryJilin UniversityChangchun 130021China Jilin Provincial Key laboratory of Straw Based Functional Materials Institute for Interdisciplinary Biomass Functional Materials StudiesJilin Engineering Normal UniversityChangchun 130052China Institute of Functional Material chemistry and National & Local United Engineering Lab for Power Battery Faculty of ChemistryNortheast Normal UniversityChangchun 130024China College of Life Science Dalian Minzu UniversityDalian 116600China

Understanding the relationship between structure and properties is critical to the development of solidstate luminescence materials with desired characteristics and performance optimization. In this work, we elaborately designed and synthesized a pair of mononuclear iridium(Ⅲ) complexes with similar structures but different degrees of cationization. [Ir2-f][2PF_(6)] with two counterions is obtained by simple Nmethylation of the ancillary ligand of [Ir1-f][PF_(6)] which is a classic cationic iridium(Ⅲ) complex. Such a tiny modification results in tremendously different optical properties in dilute solutions and powders.[Ir1-f][PF_(6)] exhibits weak light in solution but enhanced emission in solid-state as well as poly(methyl methacrylate) matrix, indicative of its aggregation-induced emission(AIE) activity. On the sharp contrary, [Ir2-f][2PF_(6)] is an aggregation-caused quenching(ACQ) emitter showing strong emission in the isolated state but nearly nonemissive in aggregation states. Benefiting from the appealing characteristics of mechanochromic luminescence and AIE behavior, [Ir1-f][PF_(6)] has been successfully applied in reversible re-writable data recording and cell imaging. These results might provide deep insights into AIE and ACQ phenomenon of iridium(Ⅲ) complexes and facilitate the development of phosphorescent materials with promising properties.

关键词： Aggregation induced-emission Cationic iridium(III)complex Counterion Mechanochromic luminescence Cell imaging

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Stereospecific hydrohalogenation reactions of electron-deficient alkynes

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Chinese Journal of chemistry 1998年第5期16卷 388-396页

作者：陆熙炎麻生明 laboratory of organometallic chemistry Shanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai 200032China

Stereospecific hydrohalogenation reactions of electron-deficient alkynes, i.e., 2-alkynoic acids, 2-alkynoates, 2-propynamides, 2-propynenitrile, 1-alkynyl phosphonates/phosphine oxides, 1-alkynyl sulfoxides/triflones, and 1-alkynyl iodonium salts with lithium or sodium halides to afford Z-alkenyl derivatives and their applications in synthesis of important intermediates as well as natural products were reviewed.

关键词： Hydrohalogenation Stereospecific synthetic applications

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FeCl_3·6H_2O-catalyzed selective reduction of allylic halides to alkenes with concomitant oxidation of benzylic alcohols to aldehydes

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Science China chemistry 2014年第2期57卷 282-288页

作者： ZHANG HouCai LIU RuiTing ZHOU XiGeng Shanghai Key laboratory of Molecular Catalysis and Innovative Materials Department of chemistry Fudan University State Key laboratory of organometallic chemistry

Iron-catalyzed direct reduction of allylic halides with benzylic alcohol was achieved,providing a new,simple,and efficient method for conducting highly regioselective *** method not only features a readily available reductant,an inexpensive catalyst,simple manipulation,and good tolerance of functional groups including nitriles,nitro,esters,and methoxyl groups,it also has mild reaction conditions and shows complete regioselectivity in that only halides sited at the allylic position are ***,this method can be applied in the selective transformation of benzylic alcohols to aromatic aldehydes without overoxidation to carboxylic acids.

关键词： selective reduction allylic halides Fe-based catalysts hydrodehalogenations benzyi alcohols

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Synthesis of 4H-chromenes by silver(Ⅰ)-catalyzed cycloaddition of ortho-quinone methides with N-allenamides

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Science China chemistry 2019年第1期62卷 80-86页

作者： Long Kong Nuligonda Thirupathi Jiong Jia Zhenghu Xu Key laboratory for Colloid and Interface chemistry of Education Ministry Department of Chemistry Shandong University State Key laboratory of organometallic chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences

Chromenes represent an important class of six-membered heterocycles and have drawn tremendous attention in recent years. In this article, we report a convenient and practical synthesis of this heterocycle by a silver(I)-catalyzed cycloaddition reaction between in situ generated ortho-quinone methides and N-allenamides. Diverse 4H-chromenes were synthesized in good to excellent yields under very mild conditions.

关键词： 4H-chromene ortho-quinone methide N-allenamide silver-catalysis cycloaddition

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HgCl_2-Catalyzed monobenzylation and monoallylation reactions of 1-phenyl-l-alkynes

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Chinese Journal of chemistry 1999年第5期17卷 531-538,427页

作者：麻生明王利莎 laboratory of organometallic chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai 200032 China

A general procedure for the HgCl2-mediated monolithiation reaction of 1-phenyl-l-alkynes was developed.

关键词： HgCl2 monolithiation 1-phenyI-l-alkynes monobenzylation monoallylation.

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Syntheses of Some New Group 4 non-Cp Complexes Bearing Schiff-base, Thiophene Diamide Ligands Respectively and Their Catalytic Activities for α-Olefin Polymerization

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Chinese Journal of chemistry 2004年第6期22卷 577-584页

作者：黄吉玲廉兵雍莉钱延龙 laboratory of organometallic chemistry East China University of Science and Technology Shanghai 200237 China

Totally sixteen new titanium and zirconium non-Cp complexes supported by Schiff-base, or thiophene diamide ligands have been synthesized. The complexes are obtained by the reaction of M(OPr-i)4 (M=Ti, Zr) with the cor-responding Schiff-base ligand in 1∶1 molar ratio in good yield. The thiophene diamide titanium complex has been prepared from trimethylsilyl amine [N,S,N] ligand and TiCl4 in toluene at 120 ℃. All complexes are well charac-terized by 1H NMR, IR, MS and elemental analysis. When activated by excess methylaluminoxane (MAO), com-plexes show moderate catalytic activity for ethylene polymerization, and complex 1f (R1=CH3, R2=Br) exhibits the highest activity for ethylene and styrene polymerization. When the complexes were preactivated by triethylaluminum (TEA), both polymerization activities and syndiotacticity of the polymers were greatly improved.

关键词： titanium or zirconium non-Cp complex TEA polymerization structure

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Direct knitting privileged molecular catalysts into recyclable single-site catalysts with enhanced activity

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Science China chemistry 2020年第4期63卷 419-420页

作者： Yong Tang State Key laboratory of organometallic chemistry Shanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai 200032China

An ideal strategy for catalyst immobilization is taking advantage of the widely well studied homogeneous molecular catalysts and transforming them directly into highly efficient and recyclable heterogeneous ***,the obtained heterogeneous catalysts often have inferior activity due to altered chemical environment around active centers and decreased mass/heat transfer[1,2].

关键词： catalysts molecular centers

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Divergent synthesis of aryl amines and dihydroquinazolinones via electrochemistry-enabled rhodium-catalyzed C–H functionalization

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中国科学:化学英文版 2023年第10期66卷 2863-2870页

作者： Yi-Kang Xing Zhen-Hua Wang Ping Fang Cong Ma Tian-Sheng Mei State Key laboratory of organometallic chemistry Shanghai Institute of Organic ChemistryUniversity of Chinese Academy of SciencesShanghai 200032China

Electrochemistry-enabled rhodium-catalyzed C–H amination and amination cyclization of arene assisted by a weakly coordinating amide have been reported. Additionally, aryl amines and dihydroquinazolinones could be obtained selectively by controlling the electric current. Mechanistic studies suggested that the amination reaction likely involves an electrochemical oxidation-induced reductive elimination of a high valent rhodium intermediate, which led to the amination reaction even proceeding smoothly at room temperature.

关键词： organic electrochemistry rhodium catalysis C-H functionalization divergent synthesis

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Synthesis and crystal structure of（C5Me4SiMe3）[（^iPrN）2CCH2SiMe3]2Y

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Journal of Rare Earths 2009年第1期27卷 18-21页

作者：陈珏王秀莲罗云杰姚英明 organometallic chemistry laboratory Ningbo Institute of TechnologyZhejiang University Department of chemistry and Chemical Engi-neering Suzhou University

Reaction of（C5Me4SiMe3）Y（CH2SiMe）2（THF） with two equivalents of iPrN=C=NiPr in hexane at room temperature afforded a mixed-ligand yttrium complex（C5Me4SiMe3）（iPrN）2CCH2SiMe32Y.X-ray diffraction revealed that the center metal was nine-coordinated by one cyclopentadienyl ring and two amidinate ligands, and adopted a four-legged piano stool geometry.

关键词： organo yttrium complex insertion reaction crystal structure rare earths

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Catalytic asymmetric borane reduction of prochiral ketones using chiral camphor-derived mercapto-alcohols

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Chinese Journal of chemistry 1998年第3期16卷 284-288页

作者：周永贵侯雪龙戴立信 laboratory of organometallic chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai 200032 China

Easily available D-(+)-camphor-derived chiral mercapto-alcohols 2 and 3 were employed for catalytic asymmetric borane reduction of aromatic ketones. Moderate enantioselectivities with e.e. 20.2–72.1% were obtained wi... 详细信息

关键词： Mercapto-alcohol ketone asymmetric borane reduction

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