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Science china chemistry 2010年第10期53卷 2112-2117页

作者： WANG PengFei, DUAN Yan & ZHENG LiMin state key laboratory of coordination chemistry coordination chemistry Institute, school of chemistry and chemical engineering, nanjing university, nanjing 210093, china 1. state key laboratory of coordination chemistry coordination chemistry Institute School of Chemistry and Chemical Engineering Nanjing University Nanjing 210093 China

The reactions of 6-phosphononicotinic acid (pnaH3) and metal salts result in three new compounds, namely, M(pnaH)-(H2O)3·H2O [M = Co(Ⅱ) (1), Ni(Ⅱ) (2), Zn(Ⅱ) (3)]. These compounds are isostructural and contain 21 helical chains made up of corner-sharing {MO5N} octahedra and {PO3C} tetrahedra. The chains are further connected by extensive hydrogen bonds to form a three-dimensional supramolecular structure. Magnetic studies reveal that dominant antiferromagnetic interactions are mediated in both 1 and 2. Interestingly the dehydrated compound 1 shows metamagnetic behavior at low temperature.

关键词： carboxylate-phosphonate coordination polymer magnetic property metamagnetism

Syntheses,crystal structures and properties of three novel coordination polymers with tripodal imidazole-containing ligands and benzenetetracarboxylate

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Science china chemistry 2010年第10期53卷 2164-2169页

作者： SU Zhi, FAN Jian & SUN WeiYin state key laboratory of coordination chemistry nanjing National laboratory of Microstructures coordination chemistry Institute, school of chemistry and chemical engineering, nanjing university, nanjing 210093, china 1. state key laboratory of coordination chemistry nanjing National laboratory of Microstructures coordination chemistry Institute School of Chemistry and Chemical Engineering Nanjing University Nanjing 210093 China

Three novel coordination polymers, [Ni2(tib)2(btec)]·2H2O (1), [Co2(tib)2(btec)]·2H2O (2) and [Zn4(tib)2(btec)Cl4]·2H2O (3), have been synthesized by using mixed ligands of 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,2,4,5-benzenetetracarboxylic acid (H4btec) under hydrothermal conditions. Complexes 1 and 2 have the same structure and are rare three-dimensional (3D) self-penetrating (3,4,5)-connected nets, while complex 3 is an unprecedented (3,4)-connected 3D net. The different structures of 1 (2) and 3 are ascribed to the distinct coordination geometry of the metal centers. The thermal stability and photoluminescence property of the complexes were investigated.

关键词： coordination polymer self-penetration crystal structure thermal stability photoluminescence property

Two bimetallic W(Ⅳ)-Mn(Ⅱ) complexes based on octacyanometallates:structures and magnetic properties

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Science china chemistry 2009年第11期52卷 1801-1807页

作者： LIU BaoLin,XIAO HongPing,SONG You & YOU XiaoZeng state key laboratory of coordination chemistry,nanjing National laboratory of Microstructures,school of chemistry and chemical engineering,nanjing university,nanjing 210093,china state key laboratory of coordination chemistry Nanjing National Laboratory of Microstructures School of Chemistry and Chemical Engineering Nanjing University Nanjing China

Two cyano-bridged heterobimetallic coordination polymers,[{Mn(dpa)2}2W(CN)8·CH3CN·4H2O]n(1)(dpa = 2,2'-dipyridylamine) and [Mn2(H2O)4{W(CN)8}·3H2O]n(2),have been synthesized and characterized structurally and magnetically.X-ray analysis shows that complex 1 is a one-dimensional(1-D) polymer of W2(CN)4Mn2 square units in which adjacent square fragments are interlinked by sharing [W(CN)8]4-moieties to form an infinite *** 2 is a three-dimensional(3-D) polymer,which shows an unforeseen structure,exhibiting a 3-D open network with a 1-D channel(ca.13.21  × 11.82 ).Fitting of the magnetic properties indicates that both polymers exhibit weakly antiferromagnetic interactions between the adjacent Mn ions.

关键词： cyano-bridged coordination polymer magnetic property manganese(Ⅱ) complex

Tripod molecules build molecular networks and open-dimer capsules by weak interactions

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Science china chemistry 2010年第4期53卷 851-857页

作者： HAN Jun1, DENG Chao1, FANG Ru1, LI YiZhi2, WANG LeYong1& PAN Yi2 1key laboratory of Mesoscopic chemistry, Ministry of Education school of chemistry and chemical engineering, nanjing university, nanjing 210093, china 2state key laboratory of coordination chemistry, nanjing university, nanjing 210093, china 1. key laboratory of Mesoscopic chemistry Ministry of Education Nanjing University Nanjing 210093 China3. School of Chemistry and Chemical Engineering Nanjing University Nanjing 210093 China2. State Key Laboratory of Coordination Chemistry Nanjing University Nanjing 210093 China

Three tripod molecules, tris(2-methoxy-5-nitrobenzyl)phosphine oxide (1), tris(2-butoxy-3-methyl-5-nitrobenzyl)phosphine oxide (2), and tris(3-nitrobenzyl)amine (TNBA), were synthesized and crystallized. The structures of 1, 2, and their comparison (TNBA) were determined by X-ray crystallography. It is noteworthy that compound 1 interacted with adjacent molecules via π-π stacking and C-H···π interactions to yield an open supramolecular network with the porosity P in 8.9%, whereas compound 2 gathered closely to form an open-dimer capsule by sixfold N-O···π and triple C-H···O interactions, which showed a rare example of a stable in, out-invertomer of phosphine inversion existing in open-dimers. A series of columns were built and arranged side by side by these weak interactions. By contrast, TNBA crystallized to form a 2D network maintained by C-H···O and C-H···πinteractions. It seems minor changes of the chemical structure may cause large differences in the crystal structure and interactions in crystal engineering.

关键词： tripod molecule supramolecular network open-dimer capsule weak interaction

Regioselective aminohalogenation of β-nitrostyrenes using NCS and NBS as nitrogen/halogen sources

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Science china chemistry 2010年第1期53卷 140-146页

作者： ZHI SanJun1,2,SUN Hao2,LIN Chen2,ZHANG GuangQian2,LI GuiGen4 & PAN Yi2,3 1 Department of chemistry,Huaiyin Normal university,Huai’an 221003,china 2 school of chemistry and chemical engineering,nanjing university,nanjing 210093,china 3 state key Lab of coordination chemistry,nanjing university,nanjing 210093,china 4 Department of chemistry and Biochemistry,Texas Tech university,Lubbock,Texas 79409-1061,USA 1. Department of chemistry Huaiyin Normal University Huai’an 221003 China2. School of Chemistry and Chemical Engineering Nanjing University Nanjing 210093 China4. Department of Chemistry and Biochemistry Texas Tech University Lubbock Texas 79409-1061 USA3. State Key Lab of Coordination Chemistry Nanjing University Nanjing 210093 China

Aminohalogenation reaction of β-nitrostyrenes with N-halosuccinimides(N-chloro and N-bromosuccinimides) has been successfully conducted by using nickel acetate as a catalyst in the presence of potassium carbonate and succinimide as *** reaction was easily performed at room temperature under nitrogen gas protection to give dihalorinaed haloamino products in good to excellent yields(60%-98%).The structure has been confirmed by X-ray crystal structure analysis.

关键词： aminohalogenation vicinal haloamines β-nitrostyrenes NBS NCS

Two novel interpenetrated zinc(Ⅱ) and cadmium(Ⅱ) coordination polymers based on 4-imidazole-benzoate:Syntheses,crystal structures and properties

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Science china chemistry 2009年第4期52卷 459-464页

作者： BAI ZhengShuai,CHEN ShuiSheng,ZHANG ZhengHua,CHEN ManSheng,LIU GuangXiang & SUN WeiYin state key laboratory of coordination chemistry,Institute of coordination chemistry,school of chemistry and chemical engineering,nanjing university,nanjing 210093,china state key laboratory of coordination chemistry Institute of Coordination Chemistry School of Chemistry and Chemical Engineering Nanjing University Nanjing China

Two novel interpenetrated coordination polymers,[Zn(IBA)2]n (1) and {[Cd(IBA)2(H2O)].4H2O}n (2),have been synthesized by using 4-imidazole-benzoic acid (HIBA) as ligand under hydrothermal con-ditions. Complex 1 crystallizes in a chiral space group and has a two-fold interpenetrated 2D network structure with (4,4) topology,while complex 2 is a 3D porous dia network with four nets interpene-trating each other. The SHG activity of 1 and the photoluminescent property of 2 have been investi-gated.

关键词： coordination polymer interpenetration crystal structure photoluminescence property

Study on specific interaction of new ferrocene-substituted carborane conjugates with hemoglobin protein

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Science china chemistry 2012年第4期55卷 594-603页

作者： WU ChunHui1,3, YE HongDe2, JIANG Hui1, WANG XueMei1 & YAN Hong2 1state key Lab of Bioelectronics (Chien-Shiung Wu Lab), Southeast university, nanjing 210096, china 2state key laboratory of coordination chemistry school of chemistry and chemical engineering, nanjing university, nanjing 210093, china 3school of Life Science and Technology, university of Electronic Science and Technology of china, Chengdu 610054, china 1. state key Lab of Bioelectronics (Chien-Shiung Wu Lab) Southeast University Nanjing 210096 China3. School of Life Science and Technology University of Electronic Science and Technology of China Chengdu 610054 China2. State Key Laboratory of Coordination Chemistry school of chemistry and chemical engineering Nanjing University Nanjing 210093 China

The interactions between the new organometallic complexes, ferrocenesubstituted dithioocarborane conjugates （denoted as FcSB1, FcSB2 and FcSBCO） and hemoglobin （Hb） are investigated by electrochemistry, fluorescence and UVvis absorption spectroscopy. The results demonstrate that FcSB1, FcSB2 and FcSBCO can bind to the heme iron center through the replacement of the weakly bound H20/02 in the distal heme pocket of Hb by their sulfur donor atoms, inducing the allosteric change from the R state （oxygenated conformation, relax） to T state （deoxygenated conformation, tense）. The binding affinity is in the order of FcSBCO〉FeSB2〉FeSB1. Moreover, the fluorescence study illustrates that the three ferrocenecarborane conjugates differently affect the quarterly and tertiary structures as well as the polarity in the surrounding of the Trp and Tyr residues in Hb. Typically, FcSB2 mainly induces alterations of the microenvironment around the 1337Trp residue which is located on the cql32 interface of Hb. Such distinct influences are attributed to the structural features of FcSB1, FcSB2 and FcSBCO containing hydrophobic ferrocenyl and carboranyl units as well as C=O group. Screening the proteinbinding behavior can signify the potential bioactivity of such molecules and may be helpful in the future development of promising multifunctional metallodrugs.

关键词： fluorescence – UV vis absorption spectroscopy – differential pulse voltammetry – biomolecular interaction – ferrocene substituted carborane conjugates – hemoglobin

The combination of benzamides/NCS as nitrogen/halogen sources for aminohalogenation of β-nitrostyrenes resulting in dichlorinated haloamides

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Science china chemistry 2010年第9期53卷 1946-1952页

作者： ZHI SanJun1,2,MEI HaiBo1,ZHANG GuangQian1,SUN Hao1,HAN JianLin1,LI GuiGen4 & PAN Yi1,3 1 school of chemistry and chemical engineering,nanjing university,nanjing 210093,china 2 school of chemistry and chemical engineering,Huaiyin Normal university,Huai’an 221003,china 3 state key laboratory of coordination chemistry,nanjing university,nanjing 210093,china 4 Department of chemistry and Biochemistry,Texas Tech university,Texas 79409-1061,USA 1. school of chemistry and chemical engineering Nanjing University Nanjing 210093 China2. School of Chemistry and Chemical Engineering Huaiyin Normal University Huai’an 221003 China4. Department of Chemistry and Biochemistry Texas Tech University Texas 79409-1061 USA3. State Key Laboratory of Coordination Chemistry Nanjing University Nanjing 210093 China

The combination of benzamide and NCS was found to be an efficient nitrogen/halogen source for aminohalogenation of β-*** reaction was convenient to carry out by using 4-dimethylaminopyridine as the catalyst,resulting in vicinal dichlorinated haloamino nitroalkanes with opposite regiochemistry to that generated from other electron-deficient olefins observed *** reaction proceeded smoothly at room temperature with good yields and excellent regioselectivities.A mechanism involving a chloronium intermediate was proposed to explain the resulting *** current system explored a new type of nitrogen sources for aminohalogenation of functionalized olefins.

关键词： aminohalogenation benzamide β-nitrostyrenes DMAP haloamides

Complex Formation between Heptakis(2,3,6-tri-O-butyl)-β-cyclodextrin with p-Nitrophenol in Heptane

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Chinese chemical Letters 1997年第7期8卷 613-614页

作者： Le Xin SONG Bao Long LI Rong JIANG Jian Gang DING and Qing Jin meng(Department of chemistry, Suzhou university. Suzhou 215006)(coordination chemistry state key laboratory, coordination chemistry Institute, nanjing university, nanjing 210093) SUZHOU UNIV DEPT CHEMSUZHOU 215006PEOPLES R CHINA nanjing UNIV INST COORDINAT CHEMSTATE KEY LAB COORDINAT CHEMNANJING 210093PEOPLES R CHINA

Heptakis(2, 3, 6-tri-o-n-butyl)- β-cyclodextrin(TB- β-CD) has been found to form an inclusion compound with p-nitrophenol in heptane. The stability constent of the inclusion compound of p-nitrophenol with TB-β-CD i... 详细信息

关键词： tri-O-butyl CD PNP cyclodextrin with p-Nitrophenol in Heptane Complex Formation between Heptakis