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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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Protein retention in dextran-grafted cation exchange chromatography:The influence of pHs,counterions and polymer structure

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Chinese Journal of Chemical Engineering 2020年第7期28卷 1904-1910页

作者： Run Liu Qinghong Shi Department of Biochemical Engineering School of Chemical Engineering and TechnologyTianjin UniversityTianjin 300350China Key Laboratory of Systems Bioengineering Ministry of EducationTianjin UniversityTianjin 300072China

Polymer-grafted ion exchange adsorbents were of great interest for the development of high-performance protein chromatography in biopharmaceutical and related fields.In this work,protein retention was systematically investigated in ion exchange chromatography packed respectively with dextran-grafted cation exchange adsorbents containing sulphopropyl(SP)ligand,SP Sepharose XL and Capto S,and non-grafted cation exchange adsorbent,SP Sepharose FF,using five proteins.With an increase of buffer p Hs,retention factors of proteins decreased among all the adsorbents,demonstrating the dominant role of electrostatic interaction for protein binding on cation exchange adsorbents.The evidences further revealed that the scattered positive charges on the surface of protein molecules,rather than net charge of protein molecule,determined protein retention on cation exchange adsorbent.Likely,counterions including NH4^+,K^+,Na^+and Mg^2+exhibited distinct influence on protein retention.It was well ascribed to solvent-mediated indirect ion-macromolecule interactions and direct ion-macromolecule interactions.Compared with SP Sepharose FF,polymer structure in dextran-grafted cation exchange adsorbents ultimately brought about different ligand distributions and smaller pore sizes,thereby regulating protein retention in cation exchange chromatography.By comparing the retention of myoglobin andβ-lactoglobulin B in SP Sepharose XL and Capto S,we reasonably speculated that the enhancement of nonelectrostatic interaction caused by reducing the space arm length was a major reason for an increasing retention factor of myoglobin in Capto S.The results in this research help us understand adsorption mechanism of protein in polymer-grafted adsorbents and give scientific guidance for the development of chromatographic materials.

关键词： Protein retention Linear gradient elution Dextran-grafted cation exchange adsorbents counterion pH

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Effect of Alkylpyrazinium counterions on the Host-guest Recognition Based on Dimethoxypillar[5]arenes

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Chemical Research in Chinese Universities 2016年第2期32卷 202-206页

作者： LIU Lijing GUO Lei ZHAO Qiuhua SHAN Yongkui LIAO Xiaojuan School of Chemistry and Molecular Engineering East China Normal University Shanghai 200241 P. R. China

In this work, we synthesized n-octylpyrazinium bromide（G-Br） and n-octylpyrazinium hexafluorophos- phate（G-PE6） as model guests and studied their host-guest complexation with 1,4-dimethoxypillar[5]arene（DMP5A）. Effect of alkylpyrazinium counterions on the host-guest recognition was investigated. Based on the lH NOESY spectra, the binding site of DMP5A with G-PF6 is the same as that of DMP5A with G-Br. However, G-PF6 forms a stronger complex with DMP5A than G-Br, owing to that hexafluorophosphate forms weaker doubly inonic H-bonds with ammonium cation than bromide ion in chloroform, which leads to some aggregates that could be dissociated with the addition of DMP5A.

关键词： Pillararene counterion Host-guest recognition Supramolecular chemistry

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A New Three-Dimensional Cyano-Bridged Ferrimagnet Built from [MoⅢ（CN）7]4- Building Block

A New Three-Dimensional Cyano-Bridged Ferrimagnet Built from...

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中国化学会第九届全国无机化学学术会议

作者： Dongqing Wu Xinyi Wang State Key Laboratory of Coordination Chemistry Collaborative Innovation Center of Advanced MicrostructuresSchool of Chemistry and Chemical EngineeringNanjing University

The search for new coordination assemblies exhibiting long-range magnetic ordering has attracted much attention over the past few decades.[1]Among them,cyanide-based transition metal materials has been one of the major research trends.Heterobimetallic assemblies derived from[M（CN）6]3-（M=Cr,Fe,Co）and[M（CN）8]3/4-（M=Mo,W）building blocks and various transition metal or rare earth metal ions have been extensively explored.[2,3]In contrast to the highly symmetrical hexa-and octacyanometallate building blocks,the geometry of the heptacyanometallates block can lead to the formation of low-symmetry extended networks,which is an important feature for designing high-temperature molecular magnets with interesting anisotropic magnetic properties.[4]While,because of handling difficulties,low-symmetry extended heptacyanometalate-based magnets are less commonly explored.By introduction dimethylamine cation,we synthesized a 3D magnet based on[MoⅢ（CN）7]4-.Magnetic investigations revealed that the compound ordered ferrimagnetically with a small hysteresis effect.

关键词： heptacyanomolybdate ferrimagnet counterion

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