吡嗪酰腙配体Cu(Ⅱ)/Ni(Ⅱ)配合物的合成、晶体结构及DNA结合性质（英文）
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摘要
合成并通过单晶衍射、元素分析及红外光谱表征了配合物[Ni(L)(HL)](SO_4)_(0.5)·3CH_3OH (1)和[Cu_2(L)_2SO_4]·1.5CH_3OH (2)的结构(HL为3-甲基-2-乙酰吡嗪苯甲酰腙)。单晶衍射实验结果表明,在配合物1中,Ni(Ⅱ)中心离子与2个酰肼配体的[ONN]配位原子组配位,形成扭曲的八面体配位构型;2的最小非对称单元中含有1个独立的双核Cu(Ⅱ)配合物分子,它的2个Cu(Ⅱ)中心由2个酰肼配体中的2个O原子桥联。每个Cu(Ⅱ)离子还与L-配体中的2个氮原子和η_2-SO_4~(2-)阴离子中的1个O原子配位,拥有扭曲的四方锥配位构型。此外,荧光光谱表明配合物和DNA的结合能力强于配体。
Two complexes, namely [Ni(L)(HL)](SO_4)_(0.5)·3 CH_3 OH(1) and [Cu_2(L)_2 SO_4]·1.5 CH_3 OH(2)(HL=3-methyl-2-acetylpyrazine benzoylhydrazone) have been synthesized and characterized by single crystal X-ray diffraction,elemental analysis and IR spectroscopy. X-ray diffraction analysis results showed that in complex 1, the center Ni(Ⅱ) ion with a distorted octahedron geometry is surrounded by two acylhydrazones with [ONN] donor set. However,complex 2 contains one discrete dimeric Cu (Ⅱ) molecule in the unit cell, in which two Cu (Ⅱ) ions were doubly bridged by two O atoms from two independent acylhydrazone ligands. Each of the Cu (Ⅱ) ions is also coordinated by two N atoms from one L-ligand and one O atom from the η_2-SO_4~(2-)anion, thus giving a distorted square pyramid coordination geometry. Moreover, the fluorescence spectra indicated that the interaction of the complexes to DNA is stronger than that of the ligand HL.
Two complexes, namely [Ni(L)(HL)](SO_4)_(0.5)·3 CH_3 OH(1) and [Cu_2(L)_2 SO_4]·1.5 CH_3 OH(2)(HL=3-methyl-2-acetylpyrazine benzoylhydrazone) have been synthesized and characterized by single crystal X-ray diffraction,elemental analysis and IR spectroscopy. X-ray diffraction analysis results showed that in complex 1, the center Ni(Ⅱ) ion with a distorted octahedron geometry is surrounded by two acylhydrazones with [ONN] donor set. However,complex 2 contains one discrete dimeric Cu (Ⅱ) molecule in the unit cell, in which two Cu (Ⅱ) ions were doubly bridged by two O atoms from two independent acylhydrazone ligands. Each of the Cu (Ⅱ) ions is also coordinated by two N atoms from one L-ligand and one O atom from the η_2-SO_4~(2-)anion, thus giving a distorted square pyramid coordination geometry. Moreover, the fluorescence spectra indicated that the interaction of the complexes to DNA is stronger than that of the ligand HL.
引文
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[3] Shanty A A, Philip J E, Sneha E J, et al. Bioorg. Med. Chem.,2016,70:67-73
[4] Castineiras A, García-Santos I, Nogueiras S, et al. J. Mol.Struct., 2014,1074:1-18
[5] HOU Xu-Feng(侯旭锋), ZHAO Xiao-Lei(赵晓雷), ZHANG Lu(张露), et al. Chinese J. Inorg. Chem.(无机化学学报),2018,34(1):201-205
[6] Olczak A, Gówka M L, Goka J, et al. J. Mol. Struct., 2007,830:171-175
[7] Popov L D, Levchenkov S I, Shcherbakov I N, et al. Russ. J.Coord. Chem., 2016,42:151-156
[8] Bi X, Sun J, Liu W L, et al. J. Inclusion Phenom. Macrocyclic Chem., 2014,80:235-242
[9] Meira C S, Filho J M D S, Sousa C C, et al. Bioorg. Med.Chem., 2018,26:1971-1985
[10]Sheldrick G M. SADABS, University of Gottingen, Germany,1996.
[11]Sheldrick G M. SHELX-97, Program for the Solution and the Refinement of Crystal Structures, University of Gottingen,Germany, 1997.
[12]Golovnev N N, Molokeev M S, Sterkhova I V, et al. Inorg.Chem. Commun., 2018,97:88-92
[13]Kubo T, Shimizu A, Sakamoto M, et al. Angew. Chem. Int.Ed., 2010,117:6722-6726
[14]MAO Pan-dong(毛盼东), ZHAO Xiao-Lei(赵晓雷), SHAO Zhi-Peng(邵志鹏), et al. Chinese J. Inorg. Chem.(无机化学学报), 2017,33(5):890-896
[15]LIN Long(林龙), LI Xian-Hong(李先宏), ZHANG Bo(张波),et al. Chinese J. Inorg. Chem.(无机化学学报), 2017,33(1):143-148