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首页> 外文期刊>Chemistry: A European journal >Multielectron redox chemistry of a neutral, NIR-active, indigo-pillared Re ~I-based triangular metalloprism
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Multielectron redox chemistry of a neutral, NIR-active, indigo-pillared Re ~I-based triangular metalloprism

机译：中性，近红外活性，靛蓝柱状Re〜I基三角形金属大分子的多电子氧化还原化学

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摘要

Self-assembled, hexarhenium(I), triangular metalloprism compound [{(CO) _3Re(μ-2)Re(CO) _3} _3(μ _3-1) _2] (3) featuring three bis-chelating pillarlike indigo dianions (μ-2), each of which connects two fac-Re(CO) _3 cores, which are interconnected by a tritopic N donor, that is, a 2,4,6-tris(4-pyridyl)-1,3,5- triazine (μ _3-1, tPyTz) ligand, has been synthesized in high yield and characterized. Metalloprism 3 exhibits a strong absorption in the near-infrared (NIR) region. The reversible, multielectron redox properties of the electrogenerated 3 ~n species, where n=3+, 0, 3-, 4-, 5-, 8-, in the visible and especially in the NIR region were investigated in THF solution by cyclic voltammetry (CV), chronocoulometry, EPR spectroscopy, and thin-layer UV/Vis/NIR spectroelectrochemistry (SEC). Stepwise, site-specific electrochemical reductions lead to the formation of a series of highly stable ion (radical) species in which electrons associated with μ-2 or μ _3-1 components of the molecule can be clearly distinguished. An EPR investigation revealed interaction of unpaired electrons with the metal nuclei (~(185,187)Re, I=5/2) in the reduced intermediates. The framework has C _2 symmetry, and accidental degeneracies suffice. Detailed theoretical calculations by structure-based DFT confirm that the triply degenerate HOMO has ≥70 % indigo character with a sizable dπ-Re character, while the LUMO is dominated by the triply degenerate indigo ligands, and the LUMO+1 by doubly degenerate tPyTz ligands. A comparison of 3 and previously reported 2,2'-bis-benzimidazolate- (BiBzlm) or alkoxy-pillared Re ~I metalloprisms indicates a very low switching potential with a potential window of less than 1 V and reversibly accessible optical properties with higher stability of the intermediates. The properties exhibited by 3 appear to be due to the slight tuning of the bridging ligand from N,N ~- to N,O ~-.
机译：自组装的六价（（I）三角金属化合物[{（CO）_3Re（μ-2）Re（CO）_3} _3（μ3-1-1）_2]（3），具有三个双螯合的柱状靛蓝阴离子（ μ-2），每个都连接两个fac-Re（CO）_3核，它们由一个三位N供体互连，即2,4,6-tris（4-吡啶基）-1,3,5 -三嗪（μ_3-1，tPyTz）配体，已经以高收率合成并进行了表征。金属元素3在近红外（NIR）区域显示出较强的吸收能力。在THF溶液中，通过循环研究了在可见光中，尤其是在NIR区域中，电生成的3〜n个物种（其中n = 3 +，0、3-，4-，5-，8，n = 3 +，0、3-，4-，5-，8）的可逆多电子氧化还原特性。伏安法（CV），计时库仑法，EPR光谱和薄层UV / Vis / NIR光谱电化学（SEC）。逐步地，特定于位点的电化学还原导致形成一系列高度稳定的离子（自由基）物种，在其中可以清楚地区分与分子的μ-2或μ_3-1组分相关的电子。 EPR调查显示还原的中间体中不成对的电子与金属核（〜（185,187）Re，I = 5/2）相互作用。该框架具有C _2对称性，并且偶然的简并性就足够了。通过基于结构的DFT进行的详细理论计算证实，三重简并的HOMO具有≥70％的靛蓝特征，具有相当大的dπ-Re特征，而LUMO由三重简并的靛蓝配体主导，而LUMO + 1由双简并的tPyTz配体主导。 。比较3种和之前报道的2,2'-双-苯并咪唑酸酯-（BiBzlm）或烷氧基-柱状Re〜I金属卟啉具有非常低的开关电势和小于1 V的电势窗，并且可逆访问的光学特性具有更高的稳定性中间体。由3显示的性质似乎是由于桥接配体从N，N〜-到N，O〜-的微调。

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