Atomistic simulation of soft porous coordination polymers

Abstract

Soft porous coordination polymers (SPCPs) are materials with exceptional potential because of their ability to incorporate the properties of nominally rigid porous materials like metal–organic frameworks (MOFs) and those of soft matter, such as polymers of intrinsic microporosity (PIMs). This combination could offer the gas adsorption properties of MOFs together with the mechanical stability and processability of PIMs, opening up a space of flexible, highly responsive adsorbing materials. In order to understand their structure and behavior, we present a process for the construction of amorphous SPCPs from secondary building blocks. We then use classical molecular dynamics simulations to characterize the resulting structures based on branch functionalities (f), pore size distributions (PSDs), and radial distribution functions and compare them to experimentally synthesized analogs. In the course of this comparison, we demonstrate that the pore structure of SPCPs is due to both pores intrinsic to the secondary building blocks, and intercolloid spacing between colloid particles. We also illustrate the differences in nanoscale structure based on linker length and flexibility, particularly in the PSDs, finding that stiff linkers tend to produce SPCPs with larger maximum pore sizes.