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Probing the potential of N-heterocyclic carbenes in molecular electronics: redox-active metal centers interlinked by a rigid ditopic carbene ligand

机译:探索分子电子中N杂环卡宾的潜力:氧化还原活性金属中心通过刚性对位卡宾配体互连

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摘要

Bimetallic homonuclear iron(II) and ruthenium(II) -heterocyclic carbene complexes have been synthesized and crystallographically analyzed. As a spacer ligand for interconnecting the two redox-active metal centers, a ditopic carbene ligand has been used that comprises two carbene sites annelated to benzene. Detailed electrochemical and spectroelectrochemical analyses of the bimetallic systems revealed that despite the potentially π-delocalized nature of the ditopic ligand, the iron centers are only moderately coupled. In the ruthenium complexes, the intermetallic interactions are very weak and the centers are electrochemically nearly independent. A model is proposed for rationalizing these observations which is based on (i) relatively weak charge delocalization in the spacer ligand and (ii) on electrostatic factors governing the metal–carbene bond.
机译:已经合成了双金属同核铁(II)和钌(II)-杂环卡宾配合物并进行了晶体学分析。作为用于互连两个氧化还原活性金属中心的间隔基配位体,已经使用了双位卡宾配位体,其包括两个与苯退火的卡宾位点。对双金属系统的详细电化学和光谱电化学分析表明,尽管双位配体可能存在π-离域性质,但铁中心仅适度耦合。在钌配合物中,金属间的相互作用非常弱,中心在电化学上几乎是独立的。提出了一个用于合理化这些观察的模型,该模型基于(i)间隔基配体中相对较弱的电荷离域和(ii)控制金属-碳键的静电因子。

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