Despite recent advances in the use of porous materials as efficient heterogeneous catalysts

which operate through effectively trapping reagents in a well-defined space, continuously

uptaking reagents to substitute products in the cavity for efficient product turnover still

remains challenging. Here, a porous catalyst is endowed with ‘breathing’ characteristics by

thermal stimulus, which can enable the efficient exchange of reagents and products through

reversible stacking from inflated aromatic hexamers to contracted trimeric macrocycles. The

contracted super-hydrophobic tubular interior with pyridine environment exhibits catalytic

activity towards a nucleophilic aromatic substitution reaction by promoting interactions

between concentrated reagents and active sites. Subsequent expansion facilitates the

exchange of products and reagents, which ensures the next reaction. The strategy of

mesoporous modification with inflatable transition may provide a new insight for construction

of dynamic catalysts.