A high-yield synthesis of [m]biphenyl-extended pillar[n]arenes for an efficient selective inclusion of toluene and m-xylene in the solid state.

[m]Bp-ExPn with a rigid and nanometer-sized cavity, as an extended version of pillar[n]arene by replacing 1,4-dimethoxybenzene monomers with biphenyl entities, was synthesized for the first time. Intriguingly, toluene and m-xylene can be stably included within the cavity of [2]Bp-ExP6, which endows these newly developed synthetic receptors with great potential in the purification of petrochemicals.