Dithienoarsinines: stable and planar π-extended arsabenzenes†

Stable planar dithienoarsinines were synthesized and structurally characterized. These compounds exhibit monomeric structures in the solution and solid states, avoiding dimerization, even in the absence of steric protection. They exhibited high global aromaticity with 14 or 22π-electron systems. In the solid state, intermolecular interactions through arsenic atoms were observed, and As⋯As interactions resulted in aggregation-induced emission enhancement properties with a significant bathochromic shift. The W(CO)₅ complex displayed a significantly distorted coordination geometry owing to arsenic cooperative stacking and hydrogen interactions, resulting in a 1D alignment of the complex. Additionally, despite their aromatic nature, dithienoarsinines undergo reactions with alkynes or benzynes to form the corresponding [4 + 2] cycloadducts. Oxygen molecules oxidize the p-position of arsinine, leading to the formation of σ-dimerized compounds while retaining the aromaticity of the arsinine ring. In contrast, oxygen attacks the phosphorus atom in phosphinine, resulting in the formation of phosphinic acid with a loss of aromaticity.