A novel luminous macrocyclic arenes, named tetraphenylethylene[3]arene 1, was conveniently synthesized by Lewis acid-promoted one-pot condensation of 1,1',4,4'-tetramethoxytetraphenylethylene and paraformaldehyde in dichloromethane at room temperature. 1 showed unique stretched hexagon structure and exhibited strong bright blue fluorescence both in solid state and in THF-H2O mixtures with water fw ≥ 60%. Especially, it was found that 1 exhibited exceptional performance in selective sensing of I- ions among other anions such as AcO-, NO3-, ClO4-, HSO4-, Br-, PF6-, H2PO4-, BF4- and CO3F3S-.

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