Topology-Directed Synthesis of Helical Phosphoniums with High Diradical Character and Polar-Dependent Electron Transfer,Chemistry of Materials

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Topology-Directed Synthesis of Helical Phosphoniums with High Diradical Character and Polar-Dependent Electron Transfer
Chemistry of Materials ( IF 7.2 ) Pub Date : 2024-08-14 , DOI: 10.1021/acs.chemmater.4c01379
Bo Yang ₁ , Suqiong Yan ₁ , Shirong Ban ₁ , Yuan Zhang ₁ , Hui Ma ₁ , Wei Huang _{1,

2}

Affiliation

Molecular topology synthesis of polycyclic aromatic hydrocarbons (PAHs) with diradical character takes root in intramolecular coupling breakthrough. Herein, we report selective Mn(III)/Cu(II)-mediated C–P and C–H bond cleavage to obtain robust donor-fused phosphoniums with helical or planar geometries and distinct cationic charges. The former helical structures incorporate a common phospha[5]helication acceptor and different arylamine donors, and the latter planar structure contains a phospha[6]dication and the same donors. These unprecedented ionic salts hold distinguishing donor–acceptor (D–A) constructions, showing unique topology-dependent optoelectronic properties. The folded helical radical ammoniums possess an extreme electron-deficient state and through-space isolation with high diradical character (y₀ = 0.989). Moreover, the tunable charge transfer (CT) and locally excited (LE) transition components facilitate diverse hybridized local and charge transfer (HLCT) in different solvents, endowing the highest emission band gap variation of 0.78 eV (∼217 nm). The fluorescence radiation could also be adjusted from blue to near-infrared regions via topology tailoring and polar-dependent excited states, which could output additional circularly polarized luminescence in a compatible chiral menthol matrix with elevated quantum efficiency and an undisturbed deep-red glow. It is worth mentioning that an atomically precise Mn(III) halide has been unprecedentedly captured and determined for C–P bond activation.

中文翻译：

具有高双自由基特性和极性依赖电子转移的螺旋鏻的拓扑定向合成

具有双自由基特征的多环芳烃（PAHs）的分子拓扑合成扎根于分子内偶联的突破。在此，我们报道了选择性 Mn(III)/Cu(II) 介导的 C-P 和 C-H 键断裂，以获得具有螺旋或平面几何形状和不同阳离子电荷的坚固的供体稠合磷鎓。前一种螺旋结构包含共同的磷酸[5]螺旋化受体和不同的芳胺供体，后一种平面结构包含磷酸[6]化和相同的供体。这些前所未有的离子盐具有独特的供体-受体（D-A）结构，显示出独特的拓扑依赖性光电特性。折叠螺旋自由基铵具有极端的缺电子态和具有高双自由基特性的空间隔离（ y ₀ = 0.989）。此外，可调电荷转移（CT）和局部激发（LE）跃迁组件促进了不同溶剂中的多种杂化局部和电荷转移（HLCT），赋予最高发射带隙变化0.78 eV（~217 nm）。荧光辐射还可以通过拓扑定制和极性相关的激发态从蓝色调整到近红外区域，这可以在兼容的手性薄荷醇基质中输出额外的圆偏振发光，具有更高的量子效率和不受干扰的深红光。值得一提的是，我们前所未有地捕获并确定了原子级精确的 Mn(III) 卤化物用于 C-P 键激活。

更新日期：2024-08-14

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