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Quadruple-stranded Eu-helicate Assembled from Bis-β-diketonate： Its Stability Towards Metal Ions

Chemical Research in Chinese Universities 2016年第4期32卷 534-538页

作者： ZHANG Lei LI Hongfeng CHEN Peng SUN Wenbin YAN Pengfei Key Laboratory of Functional Inorganic Material Chemistry Ministry of Education School of Chemistry and Materials Science Heilong/iang University Harbin 150080 P. R. China

Herein, we reported the synthesis and investigation of highly luminescent quadruple-stranded helicate （C6H 16N）4[Eu2（MBDA）4]2·3 C4H10O.4C2H 3N（ 1-Eu） [H2M B DA=N-methyl-4,4＇-b i s（4,4,4-tri fl uoro-1,3-dioxob utyl）di- phenylamine] for its stability toward metal ions in the solution. The material was characterized via X-ray crystallo- graphic technique, Fourier transform infrared（FTIR） spectroscopy and electrospray ionization quadrapole time-of- flight（ESI-TOF） mass spectrometry. The results on the luminescence quantum yields clearly demonstrate that the ligand can effectively sensitize the luminescence of the Eu3＋ ions（φoverall=15%）. Upon the addition of different metal ions（i, e., Ag＋, Cd2＋, Zn2＋, Fe3＋, A13＋ and Ni2＋） to the CH3CN solution of compound I-Eu, the emission intensities of Eu3＋ ions at 612 nm were affected to some extent, which could be attributed to the presence of ion exchanges between Eu3＋ ions and the metals ions, and the result was confirmed by ESI-TOF mass spectrometry.

关键词： helicate Fluorescence Displacement Bis-β-diketonate

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Synthesis, Crystal Structure and Photoluminescence of a New Cd-organic meso-helicate

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Chinese Journal of Structural Chemistry 2013年第8期32卷 1180-1184页

作者：杨姗姗王新芳张明星陈新肖凤祝怡刘钰君黄坤林 College of Chemistry Chongqing Normal University Department of Chemistry Dezhou University

One-pot solvothermal reaction of transition metal Cd（II ） salt with （2E,2′E）-3,3′- （（propane-1,3-diylbis（oxy））bis（2,1-phenylene））diacrylic acid （H2ppa） and 1,10-phenanthroline （phen） generates a meso-helicate, [Cd（ppa）（phen）（H2O）]2, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and photoluminescent property. The complex crys- tallizes in monoclinic, space group P21/c with a = 13.4622（7）, b = 24.8452（12）, c = 8.9314（4） A, β = 97.564（1）°, V = 2961.3（2） A3, C66H56N4O14Cd2, Mr = 1353.97, Dc = 1.518 g/cm3, μ（MoKa） = 0.789 mm-1, F（000） = 1376, Z = 2, the final R = 0.0248 and wR = 0.0667 for 4673 observed reflections （I 〉 2σ（I））. The I-D supramolecular chain is built up from the complex by π-π stacking interactions, and inter-chain hydrogen bonds prompt the I-D chains into a 2-D layer. The title compound shows strong photoluminescence with emission maximum at 2 = 445 nm upon λEx, max = 240 nm.

关键词： helicate photoluminescence cadmium supramolecular structure

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IrⅢ-Containing Metallohelices with Tuneable Photodynamic Therapy Efficacy in Cancer Cells

IrⅢ-Containing Metallohelices with Tuneable Photodynamic Th...

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中国化学会第十届全国无机化学学术会议

作者： Xuezhao Li Jinguo Wu Cheng He Chunying Duan State Key Laboratory of Fine Chemicals Dalian University of Technology

The development of promising photodynamic therapy(PDT) agents that bind to DNA for cancer treatment have drawn much more attentions recently. In this work, Ir-containing luminescent metallohelices by using a preformed facial Ir(ppy) handle which decorated with three aldehyde groups, then condensed with linear diamine spacers through dynamic covalent chemistry were designed and synthesized for the first time. Interestingly, increasing the chain length of the alkanediamine precursor resulted in an odd–even alternation between chiral helicates and achiral mesocates. After postsynthetic reduction of imine linkages, the obtained chemically robust amine-linked metallohelices showed bright green luminescent emission, and specifically stain the mitochondria of living cells. In contrast to the helicates, the mesocates showed stronger DNA-binding affinities and DNA photocleaves abilities under visible light. Importantly, the amine-linked mesocate with the longest linkers exhibited the best PDT efficiency. This study demonstrates that alterations in helicate structures can have profound effects on PDT cytotoxicity towards cancer cells.

关键词： PDT helicate Mesocate Iridium DNA-binding

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