Accumulated Lattice Strain as an Internal Trigger for Spontaneous Pathway Selection
Hubiao Huang, Hiroshi Sato, Jenny Pirillo, Yuh Hijikata, Yong Sheng Zhao, Stephen Z. D. Cheng, and Takuzo Aida
Multicomponent crystallization is universally important in various research fields including materials science as well as biology and geology, and presents new opportunities in crystal engineering. This process includes multiple kinetic and thermodynamic events that compete with each other, wherein “external triggers” often help the system select appropriate pathways for constructing desired structures. Here we report an unprecedented finding that a lattice strain accumulated with the growth of a crystal serves as an “internal trigger” for pathway selection in multicomponent crystallization. We discovered a “spontaneous” crystal transition, where the kinetically preferred layered crystal, initially formed by excluding the pillar component, carries a single dislocation at its geometrical center. This crystal “spontaneously” liberates a core region to relieve the accumulated lattice strain around the dislocation. Consequently, the liberated part becomes dynamic and enables the pillar ligand to invade the crystalline lattice, thereby transforming into a thermodynamically preferred pillared-layer crystal.
Journal of the American Chemical Society : https://pubs.acs.org/doi/10.1021/jacs.1c06854