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首页> 外文期刊>Organic Electronics >Interesting spin state properties of iron(Ⅱ) polypyridine complex substituted by fluorine: A theoretical study
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Interesting spin state properties of iron(Ⅱ) polypyridine complex substituted by fluorine: A theoretical study

机译：氟代铁（Ⅱ）聚吡啶复合物的有趣旋转状态性质：一种理论研究

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摘要

The special iron(Ⅱ) polypyridyl complex substituted by fluorine ([Fe(dftpy)_2]~(2+), dftpy = 6,6"-difluoro-2,2'; 6'2"-terpyridine) with uncommon mixed ground states has been detected recently, but the related explanation and characterization are not enough, especially for the influence of substituents. On the basis of previous studies, the key problem of mixed spin states is expected to be described very well by means of theoretical calculations. In this work, density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations have been carried out to study the characteristics of the excited states in detail. Comparing with the parent complex [Fe(tpy)_2]~(2+) (tpy = 2,2':6',2"-terpyridine) and corresponding bromine or chlorine substituted derivates, the ground states of [Fe(dftpy)_2]~(2+) stay around the mixture of singlet state and quintet state, but also there is rare high spin excited state lifetime. Among the halogen substituted complexes, [Fe(dftpy)_2]~(2+) has the shortest MLCT state lifetime of 14.0 ps which has been much longer than subpicosecond lifetime of [Fe(tpy)_2]~(2+). The reason is explored by the combination of electronic structures, absorption properties, extended transition state coupled with natural orbitals for chemical valence (ETS-NOCV) and potential energy curves (PECs). We can find that the bond lengths of Fe-N_t play a significant role on the change of metal centered (MC) ground states. With Fe-N_t extended by fluorine atoms, the quintet state becomes lower than the singlet state. Due to the deformation of structures, the interactions between metal and ligands diminish and give rise to weaker d orbital splitting than that of [Fe(tpy)_2]~(2+), but slightly impact the pairwise orbital deformation density characteristics. And the PEC of ~5MC intersects with ~(1,3)MC which renders faster non-radiative deactivation through low-lying energy crossing points.
机译：用氟代（[Fe（DFTPY）_2]〜（2+），DFTPY = 6,6“ - 氟-2,2”; 6'2“ - 吡啶）被罕见的混合地面（Ⅱ），DFTPY = 6,6”）含有罕见的铁（Ⅱ）聚吡啶酯络合物最近已检测到各种，但相关的解释和表征是不够的，特别是对于取代基的影响。在先前的研究的基础上，预计混合旋转状态的关键问题将通过理论计算来描述。在这项工作中，已经进行了密度泛函理论（DFT）和时间依赖性密度泛函理论（TDDFT）计算，以详细研究激发状态的特征。与母体复合物[Fe（TPY）_2]〜（2+）（TPY = 2,2'：6'，2“ - +吡啶）和相应的溴或氯取代衍生物，[FE（DFTPY） _2]〜（2+）围绕单态状态和QUINTET状态的混合物，也存在罕见的高旋转激发态寿命。在卤素取代的络合物中，[Fe（DFTPY）_2]〜（2+）具有最短的最短14.0 ps的MLCT状态寿命比[Fe（TPY）_2]〜（2+）的偶数寿命长得多。通过电子结构的组合，吸收特性，延伸过渡状态与天然轨道相结合的原因是探索的化学价（ETS-NOCV）和潜在的能量曲线（PEC）。我们可以发现FE-N_T的键长在金属中心（MC）地面的变化上发挥着重要作用。用氟原子延伸FE-N_T ，Quintet状态变得低于单线状态。由于结构的变形，金属和配体之间的相互作用NISH并产生比[Fe（TPY）_2]〜（2+）的轨道分裂较弱，但略微影响成对轨道变形密度特征。 〜5MC的PEC与〜（1,3）MC相交，通过低位能量过分点呈现更快的非辐射停用。

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  • 来源
    《Organic Electronics》 |2020年第10期|105884.1-105884.7|共7页
  • 作者

    Yuan Li; Xue-Wen Fan; Rong-Lin Zhong; Jie Chen; Fu-Quan Bai; Hong-Xing Zhang;

  • 作者单位

    International Joint Research Laboratory of Nano-Micro Architecture Chemistry Institute of Theoretical Chemistry College of Chemistry Jilin University Changchun 130023 People's Republic of China;

    International Joint Research Laboratory of Nano-Micro Architecture Chemistry Institute of Theoretical Chemistry College of Chemistry Jilin University Changchun 130023 People's Republic of China;

    International Joint Research Laboratory of Nano-Micro Architecture Chemistry Institute of Theoretical Chemistry College of Chemistry Jilin University Changchun 130023 People's Republic of China;

    International Joint Research Laboratory of Nano-Micro Architecture Chemistry Institute of Theoretical Chemistry College of Chemistry Jilin University Changchun 130023 People's Republic of China;

    International Joint Research Laboratory of Nano-Micro Architecture Chemistry Institute of Theoretical Chemistry College of Chemistry Jilin University Changchun 130023 People's Republic of China;

    International Joint Research Laboratory of Nano-Micro Architecture Chemistry Institute of Theoretical Chemistry College of Chemistry Jilin University Changchun 130023 People's Republic of China;

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  • 原文格式 PDF
  • 正文语种 eng
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  • 关键词

    Excited state lifetime; Halogen substituent; Quintet ground state; Iron(Ⅱ) complex;

    机译：兴奋的国家终身;卤素取代基;Quintet地面州;铁（Ⅱ）络合物;

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