Molecular and electronic structure, reduction electron transfer and coordination abilities of a polycyclic aromatic hydrocarbon (PAH) having a planar naphtho‐group fused to the corannulene bowl have been investigated for the first time using a combination of theoretical and experimental tools. A direct comparison of naphtho[2,3‐a]corannulene (C₂₈H₁₄, 1) with parent corannulene (C₂₀H₁₀, 2) revealed the effect of framework topology change on electronic properties and aromaticity of 1. The presence of two reduction steps for 1 was predicted theoretically and confirmed experimentally. Two reversible one‐electron reduction processes with the formal reduction potentials at −2.30 and −2.77 V versus Fc^+/0 were detected by cyclic voltammetry (CV) measurements, demonstrating accessibility of the corresponding mono‐ and dianionic states of 1. The products of the singly and doubly reduced napththocorannulene were prepared using chemical reduction with Group 1 metals and isolated as sodium and rubidium salts. Their X‐ray diffraction study revealed the formation of “naked” mono‐ and dianions crystallized as solvent‐separated ion products with one or two sodium cations as [Na⁺(18‐crown‐6)(THF)₂][C₂₈H₁₄⁻] and [Na⁺(18‐crown‐6)(THF)₂]₂[C₂₈H₁₄²⁻] (3⋅THF and 4⋅THF, respectively). The dianion of 1 was also isolated as a contact‐ion complex with two rubidium countercations, [{Rb⁺(18‐crown‐6)}₂(C₂₈H₁₄²⁻)] (5⋅THF). The structural consequences of adding one and two electrons to the carbon framework of 1 are compared for 3, 4 and 5. Changes in aromaticity and charge distribution stemming from the stepwise electron acquisition are discussed based on DFT computational study.

中文翻译：

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将平面基团融合到π碗中：萘并环戊二烯及其阴离子的电子和分子结构，芳香性和固态堆积

首次结合理论和实验工具研究了具有平面萘基的多环芳烃（PAH）与Corannulene碗融合的分子和电子结构，还原电子转移和配位能力。萘的直接比较[2,3-一个]碗烯（C ₂₈ ħ ₁₄，1与母碗烯（C）₂₀ ħ ₁₀，2）显示在电子性质骨架拓扑结构的变化和的芳香性的效果1。1的两个还原步骤的存在在理论上进行了预测并在实验上得到了证实。通过循环伏安法（CV）测量检测到两个可逆的单电子还原过程，其正式还原电势分别为-2.30和-2.77 V相对于Fc ^{+ / 0}，证明了1和单价阴离子的可及性。使用第1组金属进行化学还原制得单还原和双还原的萘并环戊二烯的产物，并分离为钠盐和id盐。他们的X射线衍射研究表明，以溶剂分离的离子产物形式结晶的“裸”一价阴离子和二价阴离子与一个或两个钠阳离子为[Na ⁺（18-crown-6）（THF）₂ ] [C ₂₈ H ₁₄ ^-]和[钠⁺（18-冠-6）（THF）₂ ] ₂ [C ₂₈ H ^ ₁₄ ^2-（3 ⋅THF和4 ⋅THF，分别地）。的二价阴离子1也被分离为接触离子络合物具有两个铷抗衡，[{RB ⁺（18-冠-6）} ₂（C ₂₈ H ^ ₁₄ ^2- ）]（5 ⋅THF）。添加一个和两个电子的碳骨架的结构后果1为进行比较，3，4和5。基于DFT计算研究，讨论了由于逐步电子获取而引起的芳香性和电荷分布的变化。