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首页> 外文期刊>Coordination chemistry reviews >The influence of ligand localized excited states on the photophysics of second row and third row transition metal terpyridyl complexes: Recent examples and a case study
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The influence of ligand localized excited states on the photophysics of second row and third row transition metal terpyridyl complexes: Recent examples and a case study

机译：配体局部激发态对第二排和第三排过渡金属叔吡啶基配合物光物理的影响：最新实例和案例研究

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摘要

The photophysical behavior of Ru(Ⅱ) and Os(Ⅱ) diimine complexes having complex aromatic hydrocarbon diimine ligands has received considerable attention as systems exhibiting intramolecular energy transfer to yield excited states with lifetimes much longer than the parent diimine complexes. Here we present a focused discussion of the photophysical behavior of transition metal complexes with modified terpyridyl ligands. The overview includes, as an example of approaches used to evaluate such systems, spectroscopic studies of a pair of Ru(Ⅱ) mono- and bis-terpyridyl complexes modified with vinylpyrene (Pyr-v-tpy) to have ligand localized excited states that are equal to or lower than the energy of the known MLCT state of the parent complexes, [Ru(Mpt)_2]~(3+) and [Ru(Mpt)(dien)]~(2+) (Mpt=4'-tolyl-2,2':6',2"-terpyridine, dien = diethylenetriamine). The common observation is that the presence of Pyr-v-tpy serves to lengthen the excited state lifetime of the complex through interaction of MLCT and ligand localized (IL) states. For [Ru(Pyr-v-tpy)_2]~(2+) the excited state lifetime increases by a factor of more than 10~4 relative to [Ru(Mpt)_2]~(2+). For [Ru(Pyr-v-tpy)(dien)]~(2+), the ~3IL state is close in energy to the MLCT state of the parent [Ru(Mpt)(dien)]~(2+) and, while the transient absorption spectrum is significantly perturbed relative to [Ru(Mpt)(dien)]~(2+), the excited state decay rate changes by only a factor of four. The long-lived excited state is formed in less than a ps, indicating strong coupling of the MLCT and ligand localized manifolds.
机译：具有复杂的芳香烃二亚胺配体的Ru（Ⅱ）和Os（Ⅱ）二亚胺配合物的光物理行为已受到相当大的关注，因为系统表现出分子内能量转移以产生具有比母体二亚胺配合物更长的寿命的激发态。在这里，我们提出了对具有修饰的吡啶基配体的过渡金属配合物的光物理行为的重点讨论。概述包括作为评估此类系统的方法的一个示例，对用乙烯基py（Pyr-v-tpy）修饰的Ru（Ⅱ）单-和双-叔吡啶基配合物对进行光谱研究，以使配体局部激发态为等于或低于母体复合物[Ru（Mpt）_2]〜（3+）和[Ru（Mpt）（dien）]〜（2+）的已知MLCT状态的能量（Mpt = 4'- tolyl-2,2'：6'，2“ -terpyridine，dien = diethylenetriamine）。常见的观察结果是，Pyr-v-tpy的存在可通过MLCT和局部配体的相互作用延长复合物的激发态寿命。对于[Ru（Pyr-v-tpy）_2]〜（2+），激发态寿命相对于[Ru（Mpt）_2]〜（2+）增长了10〜4倍以上。 。对于[Ru（Pyr-v-tpy）（dien）]〜（2 +），〜3IL状态的能量与父级[Ru（Mpt）（dien）]〜（2+）的MLCT状态接近。并且，尽管相对于[Ru（Mpt）（dien）]〜（2+），瞬态吸收光谱受到显着扰动，但激发态衰减率却发生了变化。 s只有四分之一。不到ps即可形成长寿命的激发态，表明MLCT和配体局部流形的强耦合。

著录项

  • 来源
    《Coordination chemistry reviews》 |2015年第1期|100-109|共10页
  • 作者

    Jing Gu; Yong Yan; Brian J. Helbig; Zhuangqun Huang; Tianquan Lian; Russell H. Schmehl;

  • 作者单位

    Department of Chemistry, Tulane. University, New Orleans, LA 70118, United States,Chemical and Materials Sciences, National Renewable Energy Laboratory, Golden, CO 80401, United States;

    Department of Chemistry, Tulane. University, New Orleans, LA 70118, United States,Chemical and Materials Sciences, National Renewable Energy Laboratory, Golden, CO 80401, United States;

    Department of Chemistry, Tulane. University, New Orleans, LA 70118, United States;

    Department of Chemistry, Emory University, Atlanta, GA 30322, United States;

    Department of Chemistry, Emory University, Atlanta, GA 30322, United States;

    Department of Chemistry, Tulane. University, New Orleans, LA 70118, United States;

  • 收录信息 美国《科学引文索引》(SCI);美国《生物学医学文摘》(MEDLINE);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    Ruthenium; Terpyridyl complexes; Intraligand; Transient absorption; Diethylenetriamine; Excited state lifetime; MLCT; ILCT;

    机译：钌;联吡啶配合物;配位体瞬态吸收二亚乙基三胺;兴奋状态寿命;MLCT;白细胞介素;

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