Ruthenium(II) complexes of 1,12-diazaperyiene and their interactions with DNA

Ruthenium(II) complexes of 1,12-diazaperyiene and their interactions with DNA
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DOI:
10.1021/ic0485965
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发表时间:
2005-08-22
影响因子:
4.6
通讯作者:
Thummel, RP
Thummel, RP
中科院分区:
化学2区
文献类型:
--
作者:
Chouai, A;Wicke, SE;Thummel, RP

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合成了四种配体1,12-二氮杂萘(DAP)的配合物[Ru(bpy)(n)(DAP)(3-n)](2+)和[Ru(DAP)(3)](2+)。[Ru(DAP)(3)](2+)配合物经X-射线衍射分析表明,配合物具有螺旋桨状结构,并具有明显的π-堆积相互作用.三种Ru(II)配合物显示出自洽的光电性质,在333-468 nm范围内具有类似的配体中心π-π(*)吸收,并且与DAP相关的MLCT带随着DAP配体的数目从1变化到3而强度增加并且能量降低。观察到与DAP嵌入DNA一致的减色性和粘度变化,并且对于混合配体络合物,测量的结合常数在1.4-1.6 x 10(6)M-1的范围内。此外,配合物[Ru(bpy)(2)(DAP)](2+)在可见光照射下能光切割质粒DNA。
Four complexes of the ligand 1,12-diazaperylene (DAP) have been prepared, [Ru(bpy)(n)(DAP)(3-n)](2+) where n = 0-2 and [Ru(DAP)(3)](2+). The [Ru(DAP)(3)](2+) complex was characterized by X-ray analysis and was found to exhibit the expected propeller-like structure with significant intermolecular pi-stacking interactions. The three Ru(II) complexes showed self-consistent optoelectronic properties with similar ligand-centered pi-pi(*) absorptions in the range of 333-468 nm and MLCT bands associated with the DAP which increased in intensity and decreased in energy as the number of DAP ligands varied from 1 to 3. Hypochromicity and viscosity changes were observed that were consistent with DAP intercalation into DNA, and binding constants were measured in the range of 1.4-1.6 x 10(6) M-1 for the mixed ligand complexes. Furthermore, the complex [Ru(bpy)(2)(DAP)](2+) was found to photocleave plasmid DNA upon irradiation with visible light.