一种新型双吡啶悬臂Mn(Ⅱ)配合物的合成、晶体结构及DNA结合能力研究

摘要/Abstract

摘要： 通过3,3′-((乙烷-1,2-二基双(2-甲基吡啶杂氮二基)双(亚甲基))双(2-羟基-5-甲基苯甲醛)与2-羟基-1,3-丙二胺的缩合反应得到一种具有双吡啶悬臂的双核锰配合物。通过X射线单晶衍射确定了该配合物结构,结果显示其分子式为[Mn₂(C₃₇H₄₃N₆O₆)]·(ClO₄)₂。该配合物属于单斜晶系,P2₁/c空间群,晶胞参数为:a=1.096 50(19) nm, b=1.419 5(3) nm, c=3.109 4(5) nm, β=108.153(5)°。进一步分析表明两个二价锰离子分别与(N_amine)₂(N_imine)₂O₃和(N_imine)₂O₄体系配位,它们与配位原子形成的几何构型分别是十面体和扭曲的八面体。两个中心锰离子距离为0.331 6 nm,由酚氧原子和醋酸根共同桥联。另外,本文也利用伏安法和黏度法对该配合物与小牛胸腺DNA的结合能力进行研究,实验结果表明它们之间的结合方式为弱的插入作用。

关键词: 双核锰配合物, 大环金属配合物, 晶体结构, DNA结合能力

Abstract: A new dinuclear manganese(Ⅱ) complex with bis-pyridine pendant-arms was synthesized by condensation between 3,3′-((ethane-1,2-diylbis((pyridin-2-ylmethyl)azanediyl)) bis(methylene))bis(2-hydroxy-5-methylbenzaldehyde) and 2-hydroxy-1,3-diaminopropane in the presence of manganese(Ⅱ). The complex was determined by X-ray diffraction single crystal structure analysis, and the corresponding formula is [Mn₂(C₃₇H₄₃N₆O₆)]·(ClO₄)₂. The results indicate that the complex crystallizes in monoclinic, space group P2₁/c, with a=1.096 50(19) nm, b=1.419 5(3) nm, c=3.109 4(5) nm, β=108.153(5)°. The crystal structure shows that the two manganese(Ⅱ) ions in the phenolbased macrocyclic dinuclear complex are coordinated with (N_amine)₂(N_imine)₂O₃ and (N_imine)₂O₄ sites, the corresponding geometry around each manganese(Ⅱ) center are decahedron and distorted octahedron. Two manganese(Ⅱ) centers are equivalently bridged by the phenolic oxygens and an acetate radical with the intermetallic separation of 0.331 6 nm. Moreover, the binding ability of the complex toward calf thymus DNA were analyzed by voltammetric and viscosity method, which indicate the bonding mode between them is weak intercalation.

Key words: dinuclear manganese(Ⅱ) complex, macrocyclic metal complex, crystal structure, DNA binding ability

中图分类号:

O641.4

王洋, 李铭, 吴宇, 闫俊涛, 毛佳伟. 一种新型双吡啶悬臂Mn(Ⅱ)配合物的合成、晶体结构及DNA结合能力研究[J]. 人工晶体学报, 2022, 51(7): 1220-1226.

WANG Yang, LI Ming, WU Yu, YAN Juntao, MAO Jiawei. Synthesis, Crystal Structure, DNA Binding Ability of a New Bis-Pyridine Pendant-Arms Mn(Ⅱ) Complex[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(7): 1220-1226.

参考文献

[1] VASHISTHA V K, KUMAR A. Kinetic and biological studies of nickel(Ⅱ) and copper(Ⅱ) macrocyclic complexes[J]. Russian Journal of Inorganic Chemistry, 2021, 66(6): 834-838.
[2] VASHISTHA V K, KUMAR A, TEVATIA P, et al. Synthesis, characterization, electrochemical and antimicrobial studies of iron(Ⅱ) and nickel(Ⅱ) macrocyclic complexes[J]. Russian Journal of Electrochemistry, 2021, 57(4): 348-356.
[3] LICOCCIA S, PAOLESSE R. Structure and bonding[M]. Rome, Italy: University of Rome Tor Vergata, 1995: 73-75.
[4] ZHOU Y H, XU Y, TAO Q L, et al. Syntheses, crystal structures and properties of zinc(Ⅱ), cadmium(Ⅱ) and cobalt(Ⅱ) coordination complexes based on 2, 4-dichlorophenoxyacetic acid and different imidazole-containing ligands[J]. Journal of Inorganic and Organometallic Polymers and Materials, 2020, 30(7): 2376-2385.
[5] KUANG J Q, ZHUANG J Q, ZHOU J, et al. Synthesis and structures of two three-dimensional hybrid materials based on vanadium polyoxoanions and macrocyclic metal complexes[J]. Transition Metal Chemistry, 2019, 44(3): 263-268.
[6] POUR S R, ABDOLMALEKI A, DINARI M. Immobilization of new macrocyclic Schiff base copper complex on graphene oxide nanosheets and its catalytic activity for olefins epoxidation[J]. Journal of Materials Science, 2019, 54(4): 2885-2896.
[7] PYLE A M, REHMANN J P, MESHOYRER R, et al. Mixed-ligand complexes of ruthenium(Ⅱ): factors governing binding to DNA[J]. Journal of the American Chemical Society, 1989, 111(8): 3051-3058.
[8] KOU H Z, WANG Y, DING P P, et al. A new macrocyclic heterobinuclear Cu(Ⅱ)-Zn(Ⅱ) complex: synthesis, crystal structure, phosphate hydrolysis, and DNA binding studies[J]. Journal of Coordination Chemistry, 2019, 72(10): 1683-1696.
[9] DING P P, WANG Y, KOU H Z, et al. Synthesis of heterobinuclear Cu(Ⅱ)-Ni(Ⅱ) complex: structure, CT-DNA interaction, hydrolytic function and antibacterial studies[J]. Journal of Molecular Structure, 2019, 1196: 836-843.
[10] 王俊伟,任建国,周保娟,等.2,2’-联吡啶In(Ⅲ)配合物与DNA作用的电化学研究[J].电化学,2008,14(1):71-75.
WANG J W, REN J G, ZHOU B J, et al. Study on the binding mode of in(bpy)Cl₃·H₂O with DNA by the methods of electrochemistry[J]. Electrochemistry, 2008, 14(1): 71-75(in Chinese).
[11] ZHONG W Y, YU J S, LIANG Y Q. Chlorobenzylidine-herring sperm DNA interaction: binding mode and thermodynamic studies[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2003, 59(6): 1281-1288.
[12] FEI B L, SUN W Y, YU K B, et al. Construction of co-ordination networks of 1, 6-bis(4′-pyridyl)-2, 5-diazahexane with silver(I) and copper(I). Structural diversity through change in metal ions and counter ions[J]. Journal of the Chemical Society, 2000(5): 805-811.
[13] WANG Q, WILSON C, BLAKE A J, et al. The one-pot halomethylation of 5-substituted salicylaldehydes as convenient precursors for the preparation of heteroditopic ligands for the binding of metal salts[J]. Tetrahedron Letters, 2006, 47:8983-8987.
[14] SMART and SAINT. Area detector control and integration software[M]. Madison, USA: Siemens Analytical X-Ray Systems, Inc., 1996.
[15] SHELDRICK G M. SHELXTL V5.1: software reference manual[M]. Madison, USA: Bruker AXS, Inc., 1997.
[16] LACHKAR M, GUILARD R, ATMANI A, et al. Synthesis of new binucleating cylindrical macrotricyclic ligands where two cyclam rings are in a face-to-face conformation. characterization of their dicopper(Ⅱ) and dinickel(Ⅱ) complexes[J]. Inorganic Chemistry, 1998, 37(7): 1575-1584.
[17] KHANMOHAMMADI H, ARABAHMADI R, ABNOSI M H, et al. Synthesis, crystal structure, spectral and biological studies of CuII-MII(M=Zn and Pb) heterodinuclear complexes of new phenol-based macrocyclic ligands[J]. Polyhedron, 2007, 26(17): 4963-4970.
[18] CHEN Y F, WEI L, BAI J L, et al. Two dinuclear Schiff-base complexes: synthesis, characterization, and biological activity[J]. Journal of Coordination Chemistry, 2011, 64(7): 1153-1164.
[19] 李慧玲,杨敏,孙金,等.一例含阴离子水簇的钴配合物的合成、结构及理论研究[J].人工晶体学报,2021,50(12):2293-2299.
LI H L, YANG M, SUN J, et al. Synthesis, crystal structure and theory studies of a cobalt complex with anion-water cluster[J]. Journal of Synthetic Crystals, 2021, 50(12): 2293-2299(in Chinese).
[20] MAO J W, ZHOU H, CHEN Y F, et al. Synthesis, structure, DNA interaction, and hydrolytic function toward bis(p-nitrophenyl) phosphate of a heterobinuclear macrocyclic complex[J]. Transition Metal Chemistry, 2012, 37(4): 385-391.
[21] Babua M S S, Krishnab P G, Reddya K H, et al. Synthesis, characterization, electrochemical studies, DNA binding, and cleavage activity of mixed copper(II) oxime DMSO complexes[J]. Main Group Chemistry, 2009, 8(2):101-114.
[22] CHENG Q R, CHEN J Z, ZHOU H, et al. Syntheses, crystal structures, and properties of two macrocyclic dinuclear Ni(Ⅱ) complexes bearing 2-pyridylmethyl pendant-arms[J]. Journal of Coordination Chemistry, 2011, 64(7): 1139-1152.
[23] HONG X L, REN J M. Synthesis, characterization and DNA-binding properties of [Ru(dipn)(tpy)](ClO₄)₂ compared with those of its series compounds[J]. Chinese Journal of Inorganic Chemistry, 2011, 27(4): 785-790.
[24] XU X H, BARD A J. Immobilization and hybridization of DNA on an aluminum(Ⅲ) alkanebisphosphonate thin film with electrogenerated chemiluminescent detection[J]. Journal of the American Chemical Society, 1995, 117(9): 2627-2631.
[25] HU H, CHEN Y F, ZHOU H, et al. Synthesis, crystal structure, and DNA cleavage activity of a dinuclear nickel(Ⅱ) complex with a macrocyclic ligand[J]. Transition Metal Chemistry, 2011, 36(4): 395-402.
[26] PAN Z Q, DING K, ZHOU H, et al. Syntheses, structures and properties of dinickel(Ⅱ) macrocyclic complexes with two 2-thiophenoethyl pendant arms[J]. Polyhedron, 2011, 30(13): 2268-2274.
[27] SHAH A, ZAHEER M, QURESHI R, et al. Voltammetric and spectroscopic investigations of 4-nitrophenylferrocene interacting with DNA[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2010, 75(3): 1082-1087.