Role of additives and solvents in the synthesis of chiral isoreticular MOF-74 topologies

Abstract

Chiral induction is a simple and inexpensive approach to synthesise chiral metal–organic frameworks, even when using achiral building-blocks. The challenge lies in selecting the proper chiral inductor. This can only be achieved upon understanding the mechanism behind the chirality transfer from the chiral guest to the achiral MOF. In this work, the role of two types of chiral additives and different solvents was investigated in the crystallization of isoreticular MOF-74. We show that pyrrolidone-based solvents can interact with the framework walls and influence the thermal stability of the MOF. The role of the different chiral additives is related to the strength of their interaction with the MOF. Unlike cinchona alkaloids that have weak interactions with the framework, L- or D-trans-4-hydroxyproline (L- or D-Hyp) can strongly bind to the Zn²⁺ metal centres and cause the twisting of the organic linker. Moreover, L- and D-Hyp additives can affect the IRMOF-74 nucleation process depending on their concentration and handedness.