Catalytic manipulation of reversibility and irreversibility in a supramolecular reaction network to control the self-assembly outcome

Catalysis is a key strategy for enhancing the yields and selectivities of desired products in both living systems and industry. Catalysts do not affect the reaction outcome of simple reversible reactions; they only accelerate equilibration. Herein, we report that catalysis greatly improves the self-assembly yield. In the presence of ReO₄⁻ as the catalyst, the M₆L₄ square-based pyramid (SP) was almost quantitatively assembled, whereas the yield was only 24% without catalysis. Experimental and theoretical analyses of the self-assembly revealed that M₃L₃ and M₄L₃ triangle species were trapped without ReO₄⁻, that in the presence of the catalyst, the conversion of the trapped species was indirectly promoted by greater acceleration of the late stage of the self-assembly, and that local reaction loops involving SP prevented global equilibration to attain a metastable state.