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A pillar[5]arene and 1,5-dioxynaphthalene-containing crown ether fused bicyclic host molecule 1 was synthesized.The pillar[5]arene and the 1,5-dioxynaphthalene-based crown ether subunits in 1 were found to selectively recognize different kinds of guest molecules.For instance,1,4-dicyanobutane G1 by the pillar[5]arene unit and paraquat G2 by the crown ether unit,respectively.