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多生色团阵列围绕三蝶烯支架排列:合成与光物理。

Multichromophoric arrays arranged around a triptycene scaffold: synthesis and photophysics.

机构信息

Laboratoire de Chimie Organique et Spectroscopies Avancées (ICPEES-LCOSA), ECPM, UMR 7515 au CNRS, 25 rue Becquerel, 67087 Strasbourg, Cedex 02, France.

出版信息

Inorg Chem. 2013 Aug 5;52(15):8653-64. doi: 10.1021/ic400809a. Epub 2013 Jul 19.

DOI:10.1021/ic400809a
PMID:23869646
Abstract

Here we report on the synthesis, characterization, and photophysics of multichromophoric arrays based on a triptycene scaffold that acts as a bridging ligand for Ir(III) and Os(II) satellite active components. The triptycene scaffold not only furnishes a rigid star-shaped 3D displacement of the metallic units in space but also plays an active role in the energy cascade. The transition metal complexes have been designed in order to display an ideal cascade in their lowest excited state energy levels. For this purpose, a novel Ir(III) complex containing two dbpz (dibenzo[a,c]phenazine) ligands (Ir) has been synthesized. The key step in the synthesis of the array was the final cross-coupling between the mixed complex IrF-Os and Ir, providing the target heterotrinuclear complex IrF-Ir-Os. The photophysical properties of models confirmed the appropriate energy displacement of the single chosen active units, in the order triptycene > IrF > Ir > Os, and fast and efficient energy transfer processes leading to the final population of the Os-based triplet level have been evidenced. The reported arrays can be considered as efficient antenna systems with an absorption range extending up to 700 nm, where the triptycene bridging ligand provides both a structural and a photophysical function.

摘要

在这里,我们报告了基于三并苯支架的多发色团阵列的合成、表征和光物理性质,该支架作为铱(III)和锇(II)卫星活性组件的桥联配体。三并苯支架不仅提供了金属单元在空间中的刚性星形 3D 位移,而且在能量级联中也发挥了积极作用。为了在其最低激发态能级中显示理想的级联,设计了过渡金属配合物。为此,合成了一种含有两个 dbpz(二苯并[a,c]吩嗪)配体的新型铱(III)配合物(Ir)。该阵列合成的关键步骤是混合配合物 IrF-Os 和 Ir 之间的最终交叉偶联,提供了目标杂核配合物 IrF-Ir-Os。模型的光物理性质证实了单个所选活性单元的适当能量位移,顺序为三并苯 > IrF > Ir > Os,并且已经证明了导致最终 Os 基三重态水平占据的快速和有效的能量转移过程。报道的阵列可以被认为是具有高效天线系统,吸收范围扩展至 700nm,其中三并苯桥联配体提供了结构和光物理功能。

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