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Synthesis, Crystal Structure and DNA Interaction of Mononuclear Osmium Complexes
Author NameAffiliationE-mail
ZHAO Ya-Chen School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China  
LI Ji School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China  
HU Jiong-Sheng School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China  
LIU Lu School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China  
WANG Meng-Meng School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China  
SU Zhi School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China  
QIAN Yong School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China liuhongke@njnu.edu.cn 
Peter J. Sadler Department of Chemistry, University of Warwick, Coventry CV4 7AL, UK  
LIU Hong-Ke School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China yongqian@njnu.edu.cn 
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.
Keywords: osmium-arene complex  crystal structure  interaction with DNA
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ZHAO Ya-Chen,LI Ji,HU Jiong-Sheng,LIU Lu,WANG Meng-Meng,SU Zhi,QIAN Yong,Peter J. Sadler,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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Chinese Journal of Inorganic Chemistry