Elementary Steps in Gold Photocatalysis

黄金光催化的基本步骤

基本信息

项目摘要

Despite great progress, many key steps in photocatalysis involving dinuclear gold(I) complexes or mononuclear gold(III) complexes remain poorly understood. A detailed understanding of elementary reactions and key intermediates is therefore crucial to conceptually design new synthetic routes. As such, the formation of free “alkynyl radicals” in the reaction of dinuclear gold complexes with iodo-substituted alkynes remains highly doubtable. Therefore, a central question involves the origin of such “alkynyl radical”-derived products and other present reactive species. In this regard the formation of gold-alkynyl species could be feasible. Thus, the exact mechanistic steps need to be elucidated.Gold-catalyzed electron transfer mechanisms were already proposed for dinuclear gold complexes as well as gold(III) complexes. In case of the dinuclear complex which does not absorb the light of blue LEDs, a base is necessary in order to form a gold-base aggregate so that the use of highly energetic UVA light can be avoided. The nature of this intermediate still needs to be clarified. For this, a combined experimental/computational approach is required. Experimental mechanistic studies consist of in situ spectroscopy, stoichiometric control experiments, fluorescence quenching experiments and isolation of key intermediates. In this regard, isolation of key intermediates could be achieved by modification of the substrates or metal complex guided by a theoretical approach. With a theoretical description of the photocatalytic behavior of dinuclear gold complexes being rare in comparison to their experimental application, a comprehensive computational protocol will first be developed. This not only enables the investigation of the energetics of such reaction mechanisms but also the calculation of excited state properties. This will be employed for the identification of photoactive intermediates and for the thorough evaluation of the subsequent catalytic steps within dinuclear Au-photocatalysis. Key features within this examination of the catalytic cycle will be the prediction of spectroscopic signatures of suspected intermediates for experimental verification as well as the computation of the energetic profile of the mechanism. Furthermore the protocol will be instrumental for the systematic theoretical elucidation of differences between SET and EnT mechanisms in dinuclear gold photocatalysis.
尽管取得了很大的进展,但涉及双核金(I)配合物或单核金(III)配合物的许多关键步骤仍然知之甚少。因此,对基元反应和关键中间体的详细了解对于概念性地设计新的合成路线至关重要。因此,在双核金配合物与碘取代的炔反应中形成自由的“炔基”仍然是非常值得怀疑的。因此,一个中心问题涉及这种“炔基自由基”衍生的产物和其他现有的反应性物种的起源。在这方面,金-炔基物质的形成可能是可行的。金催化的电子转移机制已经被提出用于双核金配合物以及金(III)配合物。在不吸收蓝色LED的光的双核络合物的情况下,需要碱以形成金基聚集体,从而可以避免使用高能UVA光。这种中间体的性质仍需澄清。为此,需要结合实验/计算方法。实验机制研究包括原位光谱,化学计量控制实验,荧光猝灭实验和关键中间体的分离。在这方面,关键中间体的分离可以通过由理论方法指导的底物或金属络合物的修饰来实现。与双核金配合物的光催化行为的理论描述相比,它们的实验应用是罕见的,将首先开发一个全面的计算协议。这不仅使调查的能量的反应机制,但也计算激发态的性质。这将被用于识别的光敏中间体,并为后续的双核Au的催化步骤的彻底评价。在此检查的催化循环的关键功能将是预测的光谱特征的可疑中间体的实验验证,以及计算的能量分布的机制。此外,该协议将有助于系统的理论阐明的差异之间的SET和EnT机制的双核金双。

项目成果

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Professor Dr. Andreas Dreuw其他文献

Professor Dr. Andreas Dreuw的其他文献

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{{ truncateString('Professor Dr. Andreas Dreuw', 18)}}的其他基金

Quantum chemical study of the operating mechanism of the light protection protein dodecin
光保护蛋白dodecin作用机制的量子化学研究
  • 批准号:
    319193282
  • 财政年份:
    2016
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    --
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    Research Grants
Non-adiabatic dynamics of electronically excited linear polyenes: learning from small and medium-sized for long polyenes and their biological function
电子激发线性多烯的非绝热动力学:从中小型学习长多烯及其生物学功能
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    239673056
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    2013
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    --
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    Research Grants
Intermolecular Coulombic Decay in Biological Systems and Open-Shell Species
生物系统和开壳物种中的分子间库仑衰变
  • 批准号:
    221566449
  • 财政年份:
    2012
  • 资助金额:
    --
  • 项目类别:
    Research Units
Theoretisches Studium elektronisch angeregter Zustände großer Moleküle
大分子电子激发态的理论研究
  • 批准号:
    97072265
  • 财政年份:
    2008
  • 资助金额:
    --
  • 项目类别:
    Heisenberg Professorships
Entwicklung eines additiven, korrigierenden Potentials für Charge-Transfer-Zustände in zeitabhängiger Dichtefunktionaltheorie
时间相关密度泛函理论中电荷转移态的附加校正势的发展
  • 批准号:
    56439979
  • 财政年份:
    2007
  • 资助金额:
    --
  • 项目类别:
    Priority Programmes
Elektronisch angeregte Zustände großer Moleküle, Untersuchung des ultraschnellen Elektronen- und Energietransfers in biologisch relevanten Systemen
大分子的电子激发态,生物相关系统中超快电子和能量转移的研究
  • 批准号:
    5348608
  • 财政年份:
    2001
  • 资助金额:
    --
  • 项目类别:
    Independent Junior Research Groups
Ab initio Simulation of Time-Resolved X-ray Spectroscopy
时间分辨 X 射线光谱的从头算模拟
  • 批准号:
    493826649
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  • 资助金额:
    --
  • 项目类别:
    Research Grants
Photo-induced non-adiabatic dynamics of Carotenoids: a systematic investigation of small model systems towards the biological molecule
类胡萝卜素的光诱导非绝热动力学:对生物分子小模型系统的系统研究
  • 批准号:
    468734905
  • 财政年份:
  • 资助金额:
    --
  • 项目类别:
    Research Grants
C-Photo: Computational photochemistry and in silico design of MOST systems
C-Photo:计算光化学和 MOST 系统的计算机设计
  • 批准号:
    517844450
  • 财政年份:
  • 资助金额:
    --
  • 项目类别:
    Research Units

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