氨基修饰的二联吡啶钌(Ⅱ)配合物的激发态动力学
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- 英文论文题名：Ultrafast Relaxation Dynamics of Amine-Substituted Bipyridyl Complexes of Ru(Ⅱ)
- 论文作者：宋宏伟 ; 郭前进 ; 夏安东
- 英文论文作者：Hongwei Song ; Qianjin Guo ; Andong Xia ; Institute of Chemistry ; Chinese Academy of Sciences
- 年：2016
- 作者机构：中国科学院化学研究所;
- 论文关键词：钌配合物 ; 金属-配体电荷转移 ; 瞬态吸收光谱
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十四分会：化学动力学
- 语种：中文
- 分类号：O641.4
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十四分会 ; 化学动力学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：264k
- 原文格式：D
- 会议级别：全国
摘要
在本工作中我们利用飞秒和纳秒时间分辨瞬态吸收技术研究了不同数量胺取代联吡啶配体的钌配合物Ru(bpy)_n(NNbpy)_(3-n)(n=0,1,2,3)的激发态弛豫动力学。随着NNbpy配体取代数量的增加,钌配合物~1MLCT的吸收峰逐渐红移。依据含时密度泛函量化计算和纳秒时间分辨瞬态吸收的结果可知,当存在bpy配体时,~3MLCT稳定态的电子会定域到bpy配体上。当n=1,2,3时,配合物从能级较低的bpy配体态发光,而当n=0时,不含有bpy配体的配合物从能级较高的NNbpy配体态发光,从而观察到发射波长的蓝移。瞬态吸收的结果证明,杂配体金属由于存在NNbpy到bpy配体间电子转移过程,所以它们的振动弛豫时间,即三重态稳定时间相对于均配体配合物的振动弛豫时间要长。
A series of Ru(II) polypyridyl complexes were investigated by steady-state and transient absorption spectroscopy, together with DFT and TD-DFT methods. The complexes are Ru(bpy)n(NNbpy)_(3-n)(n = 0,1,2,3), where bpy is 2,2-bipyridine and NNbpy is 4,4′-bis(di-p-anisylamino)-2,2-bipyridine. Steady-state absorption spectra of these complexes show a systematic red-shift of the ~1MLCT absorption. Calculated results, nanosecond and femtosecond transient absorption measurements suggest the localization of the stabilized ~3MLCT states on bpy ligands in the first three complexes, when the ligand is presented. The femtosecond transient absorption data indicates that, the intersystem crossing occurs <200 fs. For two heteroleptic complexes, the second time constants, which assigned to the stabilization of ~3MLCT, is slower than that of the homoleptic complexes because of the interligand electron transfer.
A series of Ru(II) polypyridyl complexes were investigated by steady-state and transient absorption spectroscopy, together with DFT and TD-DFT methods. The complexes are Ru(bpy)n(NNbpy)_(3-n)(n = 0,1,2,3), where bpy is 2,2-bipyridine and NNbpy is 4,4′-bis(di-p-anisylamino)-2,2-bipyridine. Steady-state absorption spectra of these complexes show a systematic red-shift of the ~1MLCT absorption. Calculated results, nanosecond and femtosecond transient absorption measurements suggest the localization of the stabilized ~3MLCT states on bpy ligands in the first three complexes, when the ligand is presented. The femtosecond transient absorption data indicates that, the intersystem crossing occurs <200 fs. For two heteroleptic complexes, the second time constants, which assigned to the stabilization of ~3MLCT, is slower than that of the homoleptic complexes because of the interligand electron transfer.
引文
[1]Nie,H.-J.;Yang,W.-W.;Zheng,R.-H.;Shi,Q.;Chen,H.;Yao,J.;Zhong,Y.-W.Inorg.Chem.,2015(54):1272-1282.
[2]Curtright,A.E.;Mc Cusker,J.K.J.Phys.Chem.A,1999(103):7032-7041.
[2]Curtright,A.E.;Mc Cusker,J.K.J.Phys.Chem.A,1999(103):7032-7041.