| 单核锇配合物的合成、晶体结构及其与DNA的作用 |
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| 引用本文： | 赵雅晨,李季,胡炯圣,刘璐,王萌萌,苏志,钱勇,Peter J. Sadler,刘红科. 单核锇配合物的合成、晶体结构及其与DNA的作用[J]. 无机化学学报, 2018, 34(10): 1833-1840 |
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| 作者姓名： | 赵雅晨 李季 胡炯圣 刘璐 王萌萌 苏志 钱勇 Peter J. Sadler 刘红科 |
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| 作者单位： | 南京师范大学化学与材料科学学院;Department |
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| 基金项目： | 国家自然科学基金重点国际合作项目（No.21420102002）,国家自然科学基金（No.21601088,21771109,21778033）,江苏省333工程人才专项基金,江苏省六大人才高峰和江苏省自然科学基金（No.BE2013716,BK20171472）资助。 |
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| 摘 要： | 使用溶剂热合成法,以p-bitmb配体(1,4-二(1-咪唑基-亚甲基)-2,3,5,6-四甲基苯)与[(η6-cymene)Os(μ-Cl)Cl]2或[(η6-bip)Os(μ-Cl)Cl]2为原料,合成了2种单核芳基锇配合物,并利用核磁、质谱、元素分析和X射线单晶衍射等手段对配合物进行了表征。配合物1属于单斜晶系,P21/c空间群,为一个单核锇的结构。中心锇原子与2个配体p-bitmb上的氮原子以及氯原子进行配位,2个配体的另一个咪唑基团通过一个亚甲基碳原子进行连接形成咪唑嗡离子,形成一个类似"碗"状的结构。一个氯离子通过氢键装载在结构的空腔内。利用核磁共振氢谱研究了结构中亚甲基的来源,并研究了配合物在缓冲溶液中的稳定性。用紫外吸收光谱、圆二色谱以及粘度法研究了配合物与DNA的相互作用,结果表明,配合物中的亚甲基来自于溶剂二氯甲烷。配合物以嵌入的方式与CT-DNA相互作用,结合常数分别为3.222×10~4 L·mol-1 (1)和1.53×10~4 L·mol-1 (2),同时配合物会减弱DNA的碱基堆积作用并可以使DNA发生解旋。
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| 关 键 词： | 芳基锇配合物 晶体结构 DNA作用 |
| 收稿时间： | 2018-05-25 |
| 修稿时间： | 2018-06-21 |
Synthesis, Crystal Structure and DNA Interaction of Mononuclear Osmium Complexes |
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| ZHAO Ya-Chen,LI Ji,HU Jiong-Sheng,LIU Lu,WANG Meng-Meng,SU Zhi,QIAN Yong,Peter J. Sadler and LIU Hong-Ke. Synthesis, Crystal Structure and DNA Interaction of Mononuclear Osmium Complexes[J]. Chinese Journal of Inorganic Chemistry, 2018, 34(10): 1833-1840 |
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| Authors: | ZHAO Ya-Chen LI Ji HU Jiong-Sheng LIU Lu WANG Meng-Meng SU Zhi QIAN Yong Peter J. Sadler LIU Hong-Ke |
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| Affiliation: | School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China,School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China,School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China,School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China,School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China,School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China,School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China,Department of Chemistry, University of Warwick, Coventry CV4 7AL, UK and School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China |
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| Abstract: | Solvothermal reactions of a p-bitmb ligand (4-bis(1-imidazol-1-ylmethyl)-2,3,5,6-tetramethyl benzene) with[Os(arene)Cl2]2 in dichloromethane were used to yield novel mononuclear osmium complexes 1 and 2 (1, arene=p-cym; 2, arene=bip), which were fully characterized by 1H NMR, ESI-MS, elemental analysis and single-crystal X-ray diffraction analysis. X-ray diffraction revealed that 1 is a mononuclear arene-osmium complex, forming a "bowl-like" structure that belongs to monoclinic system with space P21/c. The center osmium atom is coordinated with two nitrogen atom from ligands (p-bitmb) and Cl anion, whereas other imidazole ring of ligand is connected by a-CH2-group to form a dipositive bis-imidazolium center. Cl- anion can be trapped inside the cavity of this "bowl-like" structure, forming H-bonds with the backbone. 1H NMR study showed that the source of the bridging-CH2-group is the solvent, CH2Cl2. These complexes are stable in the buffer solution confirmed by the stability study with UV-Vis spectra. Furthermore, the results of UV-Vis spectra, circular dichroism and viscosity measurements revealed significant interactions between 1, 2 and calf thymus DNA (CT-DNA) via the intercalation, reduction of the base stacking, and induction of the DNA despiralization. |
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| Keywords: | osmium-arene complex crystal structure interaction with DNA |
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