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首页> 外文期刊>Chemistry: A European journal >Self-Assembled, Kinetically Locked, Ru'-Based Metallomacrocyles: Physical, Structural, and Modeling Studies
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Self-Assembled, Kinetically Locked, Ru'-Based Metallomacrocyles: Physical, Structural, and Modeling Studies

机译：自组装，运动锁定，Ru“为基础的金属大环：物理，结构和建模研究。

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摘要

By using a "complex as ligand approach," the metal-ion-tem-plated self-assembly of heterometallic teteranuclear metallomacrocycles containing kinetically locked Ru~(II) centers is described. Depending on the metal-ion template employed in the self-assembly process,the final macrocycle can be kinetically labile or inert.Electrochemical studies reveal that the kinetically inert macrocycles display reversible Ru~(III/II) oxidation couples.Thecrystal structure of a kinetically inert Ru_2Re_2 macrocycles reveals a structurally complex palmate anion-binding pocket. Host-guest studies carried out with the same macrocyle in organic solvents reveals that the complex functions as a luminescent sensor for anions and that binding affinity and luminescent modulation is dependent on the structural nature and charge of the guest anion.Computational density functional theory (DFT) studies support the hypothesis that the luminescence of the macrocycle is from a ~3MLCT state and further suggests that the observed guest-induced luminescence changes are most likely due to modulation of nonradiative decay processes.
机译：通过使用“复合物作为配体方法”，描述了含有动力学锁定的Ru（II）中心的异金属四核金属大环化合物的金属离子镀自组装。取决于自组装过程中使用的金属离子模板，最终的大环可能是动力学不稳定的或惰性的。电化学研究表明，动力学惰性的大环表现出可逆的Ru〜（III / II）氧化对。惰性Ru_2Re_2大环化合物揭示了结构复杂的棕榈酸酯阴离子结合袋。用相同的大环在有机溶剂中进行的客体研究表明，该复合物可作为阴离子的发光传感器，结合亲和力和发光调节取决于客体阴离子的结构性质和电荷。计算密度泛函理论（DFT） ）研究支持以下假设：大环的发光来自〜3MLCT状态，并进一步表明，观察到的客体诱导的发光变化最有可能是由于非辐射衰变过程的调节所致。

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