Modular Design of Domain Assembly in Porous Coordination Polymer Crystals via Reactivity-Directed Crystallization Process

The mesoscale design of domain assembly is crucial for
controlling
the bulk properties of solids. Herein, we propose a modular design
of domain assembly in porous coordination polymer crystals via exquisite
control of the kinetics of the crystal formation process. Employing
precursors of comparable chemical reactivity affords the preparation
of homogeneous solid-solution type crystals. Employing precursors
of distinct chemical reactivity affords the preparation of heterogeneous
phase separated crystals. We have utilized this reactivity-directed
crystallization process for the facile synthesis of mesoscale architecture
which are either solid-solution or phase-separated type crystals.
This approach can be also adapted to ternary phase-separated type
crystals from one-pot reaction. Phase-separated type frameworks possess
unique gas adsorption properties that are not observed in single-phasic
compounds. The results shed light on the importance of crystal formation
kinetics for control of mesoscale domains in order to create porous
solids with unique cooperative functionality.