Figure 1 shows the normalized absorption spectra of [Ru(bpy)3-n(dpb)n]2þ (n=1-3) and [Ru(bpy)3]2þ. Comparison of these spectra can lead to the assignments of a πfπ* transition to the bpy ligand centered at 286 nm, a πfπ* ... Figure 1 shows the normalized absorption spectra of
[Ru(bpy)3-n(dpb)n]2þ (n=1-3) and [Ru(bpy)3]2þ. Comparison
of these spectra can lead to the assignments of a πfπ*
transition to the bpy ligand centered at 286 nm, a πfπ*
transition to the dpb ligand centered at both 315 and 400 nm,
and a 1MLCT transition over the visible region, in good
agreement with the previous results.8 The dpb ligand renders
the 1MLCT of [Ru(bpy)3-n(dpb)n]2þ 100 nm red-shifted
compared to that of [Ru(bpy)3]2þ. In aqueous solutions,
[Ru(bpy)3-n(dpb)n]2þ undergoes a further bathochromic shift
(Supporting Information), favorable for PDT application.
The 3MLCT emissions of [Ru(bpy)3-n(dpb)n]2þ fall in the
region of NIR (Table 1 and Supporting Information), recorded
on a Confocal Laser Micro-Raman Spectroscope (532
nm excitation). On the same instrument, an emission centered
at 619nmwas observed for [Ru(bpy)3]2þ, in linewith the result
obtained on a conventional fluorescence spectrophotometer.
The electrochemical properties of these complexes were
examined using cyclic voltammetry (Table 1 and Supporting
Information). [Ru(bpy)2(dpb)]2þ displays a reversible Ru-
(III/II) based oxidation wave at þ1.43 V versus SCE. The
0.14 V of anodic shift compared to that of [Ru(bpy)3]2þ
(þ1.29 V) may be attributed to the more electronegative
character or stronger π-accepting feature of dpb than bpy.
This is supported by the less negative reduction potential of
-0.60 V for dpb compared to -1.33 V for bpy (Table 1). For
[Ru(bpy)(dpb)2]2þ and [Ru(dpb)3]2þ, the dpb ligand-based
first reduction potentials appear at -0.50 V and -0.47 V,
respectively, in accordance with the previous results.8 The
oxidation processes of [Ru(bpy)(dpb)2]2þ and [Ru(dpb)3]2þ
are no longer reversible with the peak potentials at 1.65 and
1.64 V, respectively. Carlson and RorerMurphy ascribed the
irreversible oxidation wave of [Ru(dpb)3]2þ to the oxidation
of the dpb ligand.8
The DNA titration approach was used to examine the
binding abilities of these complexes toward calf thymusDNA
(CT-DNA). The absorption spectrum of [Ru(bpy)2(dpb)]2þ
shows negligible changes upon the addition of DNA, indicative
of a weak interaction. For [Ru(bpy)(dpb)2]2þ and
[Ru(dpb)3]2þ, the MLCT absorbance increased at first and
then decreased continuously with the addition of CT-DNA.
Such behavior was also observed for other Ru(II) complexes,
probably due to the DNA-induced complex aggregation.
3g,5,13 Thus, an EB displacement assay was carried out
to compare the DNA binding affinities of these complexes
(Table 1 and Supporting Information). The binding constants
of [Ru(bpy)(dpb)2]2þ and [Ru(dpb)3]2þ are much
higher than that of [Ru(bpy)2(dpb)]2þ, presumably due to
themore hydrophobic property of dpb than bpy (Supporting
Information)
图1示出了[Ru(bpy)3-n(dpb)n]2+(n=1-3)和[Ru(bpy)3]2+的归一化吸收谱。比较这些谱可以得出以下现象的陈述,即ZX在286nm处的bpy配体的π→π*跃迁,ZX在315和400nm处的dpb配体的π→π*跃迁,以及在可见光区的1MLCT跃迁,这和以前的结果很符合8。相比于[Ru(bpy)3]2+的吸收谱,dpb配体授予[Ru(bpy)3-n(dpb)n]2+的1MLCT以100nm的红移。在含水溶液中,[Ru(bpy)3-n(dpb)n]2+经历进一步的红移(支持信息),这有利于PDT的应用。[Ru(bpy)3-n(dpb)n]2+的3MLCT发射落在近红外区(表1和支持信息),在共焦激光显微拉曼光谱仪(532nm激发)上记录下来。在相同的仪器上,观察到了[Ru(bpy)3]2+的ZX位于619nm的发射,与在常规荧光分光光度计上得到的结果一致。
这些络合物的电化学性质用循环伏安法进行了研究(表1和支持信息)。[Ru(bpy)2(dpb)]2+在+1.43V相对于SCE下显示了可逆的基于Ru(III/II)的氧化波。相比于[Ru(bpy)3]2+(+1.29V)的0.14V的阳极偏移可以归因于dpb比bpy更大的负电特性或更强的π接受特征。这受到了dpb相比于bpy-1.33V较低的(-0.60V)负还原电位的支持(表1)。对于[Ru(bpy)(dpb)2]2+和[Ru(dpb)3]2+来说,基于dpb配体的diyi个还原电位分别出现在-0.50V和-0.47V。Carlson和Rorer Murphy把[Ru(dpb)3]2+的不可逆氧化波归因于dpb配体的氧化8。
采用了DNA滴定法来研究这些络合物对小牛胸腺DNA(CT-DNA)的结合亲和力。[Ru(bpy)2(dpb)]2+的吸收谱在添加DNA时显示出可忽略不计的变化,表明了弱的互作用。对于[Ru(bpy)(dpb)2]2+和[Ru(dpb)3]2+来说,MLCT吸光率先是增加,然后随着CT-DNA的添加而不断下降。这样的性状对于其他Ru(II)络合物也观察到了,这或许是由于DNA诱导的络合物聚集3g,5,13。因此,为了对比这些络合物的结合亲和力,进行了EB(溴化乙锭)置换测定(表1和支持信息)。[Ru(bpy)(dpb)2]2+和[Ru(dpb)3]2+的结合常数明显要高于[Ru(bpy)2(dpb)]2+的,这大概是由于dpb比bpy有更强的疏水性(支持信息)