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Spin-modulated near-infrared-Ⅰ emission in a xanthene-decorated Fe(Ⅱ) spin-crossover complex

Science China Chemistry 2025年

作者： Cheng Yi Duyong Chen Shihui Zhang Rui Cai chunying duan Yinshan Meng Tao Liu State Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials and Chemical Engineering School of Chemical Engineering Dalian University of Technology Instrumental Analysis Center Dalian University of Technology School of Chemistry Dalian University of Technology Liaoning Binhai Laboratory

Molecular materials showing synergetic coupling of near-infrared （NIR） fluorescence and spin-crossover （SCO） are promisingly applicable in in-vivo bioimaging,temperature sensing,and spintronic *** the related study faces formidable *** this work we graft the NIR fluorophore xanthene onto the dipyridyl substituted triazole ligand and construct a new Febased SCO material,{FeⅡ（ddxc-abpt）2[N（CN）2]2}(1,ddxc-abpt:（E）-4-(((3,5-di（pyridin-2-yl）-4H-1,2,4-triazol-4-yl)imino)methyl)-N,N-diethyl-2,3-dihydro-1H-xanthen-6-amine).Magnetic studies indicate that compound 1 exhibits thermally induced SCO property in both the solid and solution ***-temperature fluorescence emission spectra reveal a remarkable 7-fold increase in photoluminescence intensity upon the transition from the low-spin state at 110 K to the high-spin state at 280 K,which is the record of all reported coupled fluorescence-SCO ***-temperature ultraviolet-visible （UV-Vis）absorption spectra show a significant change in absorption intensity within the fluorescence emission window,consistent with the F?rster resonance energy transfer （FRET） ***-dependent density functional theory （TD-DFT） calculations demonstrate that the strong coupling is attributed to disrupted energy transfer between the xanthene fluorophore and high-spin *** work provides a feasible approach for expanding the synergetic SCO-fluorescence materials to the NIR-Iwavelength region,and hopefully contributes to the applications of tunable NIR-SCO molecule-based sensors and devices.

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Highly effective self-assembled porphyrin MOCs nanomaterials for enhanced photodynamic therapy in tumor

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Chinese Chemical Letters 2024年第5期35卷 302-306页

作者： Yihao Zhang Yang Jiao Xianchao Jia Qiaojia Guo chunying duan School of Chemistry Dalian University of TechnologyDalian 116024China State Key Laboratory of Fine Chemicals School of ChemistryDalian University of TechnologyDalian 116024China

Porphyrins and their derivatives are excellent photosensitizers in photodynamic therapy(PDT).The modification of porphyrin molecules into metal-organic cages(MOCs)is a viable strategy to improve their *** this work,MOC C66 based on porphyrin was synthesised by a one-pot self-assembly *** three-dimensional structure of the metal-organic cage ameliorated the aggregation and selfquenching of porphyrins and increased the molar absorption coefficient in the visible light region,which enhanced the reactive oxygen species(ROS)yield of porphyrins and effectively improved the efficiency of photodynamic *** generation ability tests in solution confirmed the improved reactive oxygen capacity of the cage,which showed greater phototoxicity to HeLa and MCF-7 cells in vitro,suggesting a new strategy for future modifications of the simple synthesis of porphyrins as photosensitizers.

关键词： Metal-organic cage Porphyrin Photodynamic therapy Reactive oxygen species Nanoparticles

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Cavity-directed nitroaromatics sensing within a carbazole-based luminescent supramolecular M2L3 cage

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Chinese Chemical Letters 2020年第1期31卷 95-98页

作者： Tianchi Feng Xuezhao Li Jinguo Wu Cheng He chunying duan State Key Laboratory of Fine Chemicals Dalian University of Technology

The design and preparation of luminescent M2L3 metal-organic cage via the coordination-driven selfassembly of carbazole-based ligand with a V-shaped geometry is *** cage Zn-L1 with an open cavity which equipped aromatic rich ligands shows the highest emission quenching efficiency towards picric acid than other nitroaromatic *** quenching ability depended on whether there formed the host-guest molecules are well explored by electrospray ionization mass spectrometry(ESIMS),and isothermal titration microcalorimetry(ITC).

关键词： Metal-organic cage Host-guest recognition Picric acid Fluorescence

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Palladium-Catalyzed Desulfitative Cross-Coupling of Sodium Arylsulfinates with Aryl Bromides and Chlorides： An Alternative Convenient Synthesis of Biaryls

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Chinese Journal of Chemistry 2013年第10期31卷 1269-1273页

作者： Chao Zhou Yarning Li Yang Lu Rong Zhang Kun Jin Xinmei Fu chunying duan State Key Laboratory of Fine Chemicals School of Chemical Engineering Dalian University of Technology Dalian Liaoning 116024 China

An alternative method for synthesis of biaryls has been developed through the Pd catalyzed desulfitative coupling reaction of sodium arylsulfinates with aryl bromides and chlorides. The procedure tolerates a variety of functional groups, such as cyano, formyl, acetyl, chloro, methoxy, trifluoromethyl and heteroaromatic unit. The desired products were obtained in moderate to excellent yields under relatively mild reaction conditions without additives, base or co-catalyst.

关键词： cross-coupling desulfination aryl bromides aryl chlorides palladium

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Synthesis, structure, and magnetic properties of a cyanide-bridged Fe(Ⅲ)-Cu(Ⅱ) bimetallic double-zigzag chain with slow relaxation of the magnetization

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Science China Chemistry 2012年第6期55卷 1018-1021页

作者： DONG DaPeng ZHENG Hui ZHAO Liang ZHUANG PengFei LIU Tao HE Cheng duan chunying State Key Laboratory of Fine Chemicals Dalian University of Technology Dalian 116012 China

Using Bu4N[Fe(Tp*)(CN)3]- (Tp* = hydrotris(3,5-dimethylpyrazol-l-yl)borate) as the building block to react with Cun and N-methylimidazole, we obtained a one-dimensional (1D) beterobimetallic cyano-bridged chain, [Fe(Tp*)(CN)3]2Cu(N- methylimidazole)2.2H20 (1). The crystal structures and magnetic studies demonstrate that complex 1 exhibits slow relaxation of the magnetization due to strong intrachain ferromagnetic coupling and weak interchain interactions.

关键词： single chain magnet double-zigzag chain ferromagnetic coupling

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Synthesis, structure, and magnetic properties of a cyanide-bridged Fe(Ⅲ)-Cu(Ⅱ) bimetallic double-zigzag chain with slow relaxation of the magnetization

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中国科学:化学 2012年第6期42卷 918-919页

作者： DONG DaPeng ZHENG Hui ZHAO Liang ZHUANG PengFei LIU Tao HE Cheng duan chunying State Key Laboratory of Fine Chemicals Dalian University of TechnologyDalian 116012Chin

Using Bu4N[Fe(Tp*)(CN)3]- (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) as the building block to react with CuII and N-methylimidazole, we obtained a one-dimensional (1D) heterobimetallic cyano-bridged chain, [Fe(Tp*)(CN)3]2Cu(N- methylimidazole)2·2H2O (1). The crystal structures and magnetic studies demonstrate that complex 1 exhibits slow relaxation of the magnetization due to strong intrachain ferromagnetic coupling and weak interchain interactions.

关键词：铁磁耦合晶体结构磁学性质磁化松弛氰化物双金属 N-甲基咪唑

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Homochiral Crystallization of Metal-Organic Silver Frameworks for Asymmetric Catalysis

Homochiral Crystallization of Metal-Organic Silver Framework...

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手性中国2014学术研讨会

作者： Xu Jing chunying duan State Key Laboratory of Fine Chemicals Dalian University of Technology

＜正＞Metal-organic frameworks（MOFs）are hybrid solids with infinite network structures built from organic bridging ligands and inorganic connecting nodes.[1,2]By incorporating three pyridine-imine bidentate chelators into a triphenylamine fragment,we realized the homochiral crystallization of silver-based MOFs by using cinchonine or cinchonidine as chiral *** on the investigation of 20 independent

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Photoactive Polyoxomatalate based Metal-Organic Frameworks for Light-Driven Acceleration of alpha-site C-H Arylation of Amino

Photoactive Polyoxomatalate based Metal-Organic Frameworks f...

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中国化学会第八届全国配位化学会议

作者： Zheng Ming chunying duan State Key Laboratory of Fine Chemicals Dalian Univeisity of Technology

An efficient photosensitizing of[γ-SiWVO]based MOF(POM-Cd-TPPA)within cage and channel was achieved via in situ synthesis under solvothermal conditions for light-driven acceleration ofα-site C-Harylation of amino[1].Single-crystal structural analysis revealed that POM-Cd-TPPA crystallized in a space group *** crystallographically independent Cdis connected by deprotonated[γ-SiWVO]polyoxoanions to generate a 3D *** ligands embedinto the structure,stabilizing the framework and generating a huge *** Cd atom adopted a six-coordinated octahedral geometry with four nitrogen atoms from four TPPA ligands positioned in the equatorial plane and two terminal oxygen atoms from two deprotonated[γ-SiWVO]polyoxoanions occupied in the axial *** polyoxoanion is connected with four Cadmiun ions throw four terminal oxygen atoms from the POM,and each TPPA is connected with three Cadmiun ions throw three Nitrogen atoms of the ligand(Figure.1).Detailed structural analysis using the PLATON software suggests that the effective free volume of POM-Cd-TPPA without the sovlent molecules is42.8%.The pores and caves of POM-Cd-TPPA are thus able to adsorb terephthalonitrile and its derivatives which are the substrates for the C-H arylation of aromatic tertiary amines(Table 1).

关键词： Polyoxomatalates Metal-Organic Frameworks Photocatalysis Arylation of Amino

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Supramolecular Catalysis Within Metal-organic Architectures

Supramolecular Catalysis Within Metal-organic Architectures

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全国第十八届大环化学暨第十届超分子化学学术讨论会

作者： Cheng He chunying duan State Key Laboratory of Fine Chemicals Dalian University of Technology

＜正＞Metal-organic supramolecular systems that constructed through the coordination of metal ions and organic linkers,represent a unique class of functional molecular containers that display interesting recognition properties and fascinating reactivity reminiscent of the natural *** architectures generating well-defined cavities provided specific inner environments for selective bonding of guest molecules and

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Merging Photocatalysis and Copper Catalysis in MOFs for Chloro trifluoromethylation of Electron-deficient Alkenes

Merging Photocatalysis and Copper Catalysis in MOFs for Chlo...

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中国化学会第八届全国配位化学会议

作者： Yusheng Shi Tiexin Zhang chunying duan State Key Laboratory of Fine Chemicals Dalian University of Technolegy

Synthesis of CF-containing compounds is of great interest because of their broad use in the pharmaceutical and agrochemical industries[1].Herein,Cu-TCA[2]was used as an effective hetero-geneous catalyst to mediate chlorotrifluoromethylation of a diversity of electron-deficient alkenes via a synergistic way under photochemical *** incorporating a photoactive triphenylamine group and a transition-metal catalyst copper into one single MOF,Cu-TCA was endowed with excellent reductive ability in the excited state and good C1 transfer property,making it as a good candidate for initiating and propagating the ATRA reaction[3].The catalytic performance has been compared with that of other MOFs with ether triphenylamine or copper paddle-wheel moieties namely MOF-150,HKUST-1 as well as ligand,copper salt and their *** experiments indicate the advantage of Cu-TCA by merging two catalytic sites in one MOF and imply the importance of electron transfer between the copper catalysis and photocatalysis in this catalytic process.

关键词： MOF photocatalysis copper catalysis chlorotrifluoromethylation

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