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首页> 外文期刊>ChemPlusChem >Ultrafast dynamics of meso-tetraphenylmetalloporphyrins: The role of dark states
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Ultrafast dynamics of meso-tetraphenylmetalloporphyrins: The role of dark states

机译：Meso-tetraphenylmetalloporlins的超快动态：黑暗状态的作用

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摘要

Studying the relaxation pathways of porphyrins and related structures upon light absorption is crucial to understand the fundamental processes of light harvesting in biosystems and many applications. Herein, we show by means of transient absorption studies, following Q- and Soret-band excitation, and aba initio calculations on meso-tetraphenylporphyrinato magnesium(II) (MgTPP) and meso-tetraphenylporphyrinato cadmium(II) (CdTPP) that electronic relaxation following Soret-band excitation of porphyrins with a heavy central atom is mediated by a hitherto disregarded dark state. This accounts for an increased rate of internal conversion. The dark state originates from an orbital localized at the central nitrogen atoms and its energy continuously decreases along the series from magnesium to zinc to cadmium to below 2.75a eV for CdTPP dissolved in tetrahydrofuran. Furthermore, we are able to directly trace fast intersystem crossing in the cadmium derivative, which takes place within (110±20)a ps. Stab in the dark: By means of transient absorption studies, following Q- and Soret-band excitation, and aba initio calculations on meso- tetraphenylporphyrinato magnesium(II) (MgTPP) and meso-tetraphenylporphyrinato cadmium(II) (CdTPP), it is shown that electronic relaxation following Soret-band excitation of porphyrins with a heavy central atom is mediated by a hitherto disregarded dark state (see picture).
机译：在光吸收时研究卟啉和相关结构的弛豫途径对于了解生物系统中的光收获的基本过程和许多应用是至关重要的。在此，我们通过瞬态吸收研究显示Q-和Soret波段溶激，和甲基苯基镁镁（II）（MGTPP）和中霉素 - 四苯基卟啉镉（II）（CDTPP）的ABA Initio计算，其电子放松用重中心原子的卟啉突出带激发由迄今为止忽略的黑暗状态介导。这占内转换率的增加。暗状态源自中央氮原子的轨道局部，其能量沿着从镁氧化锌的系列连续降低至镉至2.75AEV中溶解在四氢呋喃中的CDTPP。此外，我们能够在镉衍生物中直接追踪快速的跨越式交叉，这在PS内（110±20）。刺痛：通过瞬时吸收研究，Q-和Soret波段激发，以及在中间四苯基卟啉镁（II）（MGTPP）和中索 - 四苯基卟啉镉（II）（CDTPP）上的ABA Initio计算，是表明，通过迄今为止忽视黑暗状态介导的卟啉突出卟啉的电子弛豫介导（见图）。

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  • 来源
    《ChemPlusChem》 |2013年第10期|共8页
  • 作者

    LiangY.; BradlerM.; KlingerM.; SchalkO.; BalabanM.C.; BalabanT.S.; RiedleE.; UnterreinerA.-N.;

  • 作者单位

    Institute for Physical Chemistry and Center for Functional Nanostructures Karlsruhe Institute of;

    Lehrstuhl für BioMolekulare Optik Ludwig-Maximilians-Universit?t Oettingenstra?e 67 80538 M;

    Institute for Physical Chemistry and Center for Functional Nanostructures Karlsruhe Institute of;

    Lehrstuhl für BioMolekulare Optik Ludwig-Maximilians-Universit?t Oettingenstra?e 67 80538 M;

    Institute for Nanotechnology and Center for Functional Nanostructures Karlsruhe Institute of;

    Institute for Nanotechnology and Center for Functional Nanostructures Karlsruhe Institute of;

    Lehrstuhl für BioMolekulare Optik Ludwig-Maximilians-Universit?t Oettingenstra?e 67 80538 M;

    Institute for Physical Chemistry and Center for Functional Nanostructures Karlsruhe Institute of;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 化学;
  • 关键词

    dark states; density functional calculations; femtosecond spectroscopy; porphyrinoids;

    机译：黑暗状态;密度函数计算;飞秒光谱;卟啉曲线;

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