A combined experimental and theoretical approach to investigate the structure, magnetic properties and DNA binding affinity of a homodinuclear Cu(ii) complex

被引:23
作者
Ahamad, M. Naqi [1 ]
Shahid, M. [1 ]
Ansari, Azaj [2 ]
Kumar, Manjeet [2 ]
Khan, Ishaat M. [1 ]
Ahmad, Musheer [3 ]
Rahisuddin [4 ]
Arif, Rizwan [4 ]
机构
[1] Aligarh Muslim Univ, Dept Chem, Aligarh 202002, Uttar Pradesh, India
[2] Cent Univ Haryana, Dept Chem, Mahendergarh 123031, Haryana, India
[3] Aligarh Muslim Univ, Dept Appl Chem ZHCET, Aligarh 202002, Uttar Pradesh, India
[4] Jamia Millia Islamia, Dept Chem, New Delhi, India
关键词
EFFECTIVE CORE POTENTIALS; COPPER(II) COMPLEXES; CRYSTAL-STRUCTURE; MOLECULAR CALCULATIONS; ORTHO-HYDROXYLATION; IN-VITRO; DOCKING; LIGANDS; METAL; CLEAVAGE;
D O I
10.1039/c9nj00228f
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Herein, an antiferromagnetic homodinuclear Cu(ii) complex of propanolamine, [Cu-2(pa)(2)(OAc)(2)] (1), containing an acetate auxiliary was crystallized out. The complex was characterized by spectral, X-ray crystallographic, magnetic and DFT/TD-DFT studies. Single crystal X-ray data reveal that 1 crystallizes in the triclinic system with the P1 space group, and each Cu(ii) ion adopts a four-coordinated square planar geometry with the [N,O,O,O] donor set. The two [Cu(CH3COO)(pa)](+) units are connected through two alkoxy groups of the pa(-) ligand belonging to each unit; this results in the formation of a binuclear Cu(ii) system with the bridging Cu1-O1-Cu2 angle = 103.81 degrees and the intradimer CuCu distance = 3.022 angstrom. The experimental results obtained via the binding experiments of the present complex with DNA are in line with the theoretical results. The auxiliary acetate group and the bridged pa(-) ligand facilitate the binding tendency of the complex to DNA in the minor groove region (as confirmed by docking analysis), thereby forming stronger H-bonding interactions. The easy transfer of an electron from the HOMO of DNA to the LUMO of the complex further supports the existence of a stronger binding interaction, as confirmed by the DFT analysis. Temperature variable magnetic studies (SQUID measurements) revealed the presence of strong antiferromagnetic interactions (J = -222.4(2) cm(-1)) between two Cu(ii) nuclei in a molecule, and the presence of these interactions was further supported by theoretical studies. The larger CuCu distance and Cu-O-Cu angle are the factors behind the antiferromagnetic exchange between two Cu(ii) centers. Thus, the present study establishes that the fine tuning of structures in transition metal complexes can result in the formation of magnetically and biologically important molecules for future applications.
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收藏
页码:7511 / 7519
页数:9
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