Fusing a Planar Group to a π‐Bowl: Electronic and Molecular Structure, Aromaticity and Solid‐State Packing of Naphthocorannulene and its Anions

Abstract

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 (C₂₈ H₁₄ , 1) with parent corannulene (C₂₀ H₁₀ , 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 ][C₂₈ H₁₄^- ] and [Na⁺ (18-crown-6)(THF)₂ ]₂ [C₂₈ H₁₄^2- ] (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 (C₂₈ H₁₄^2- )] (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.