DOE OSTI2013
The research carried out within this grant focused on characterizing spin crossover (SCO) transitions, i.e., the change in spin state, in metal-organic frameworks (MOFs). MOFs are three-dimensional networks in which metal ions or clusters are connected to multidentate ligands. By combining high porosity, large surface area, guest selectivity, structural flexibility, and SCO properties, MOFs provide a promising platform for the development of multifunctional materials, such as molecular switches, memory devices, and chemical sensors. To characterize the SCO properties of MOFs at the molecular level, we have developed a hybrid Monte Carlo / molecular dynamics (MC/MD) method that builds upon the ligand field molecular mechanics (LFMM) model. Within LFMM, conventional molecular mechanics (MM) energy expressions are supplemented with an additional term that effectively represents the ligand field stabilization energy (LFSE) arising from the splitting and different occupation of the d-based molecular orbitals. LFMM thus explicitly includes energy contributions that depend on both the instantaneous coordination geometry and the electronic structure of the metal centers. In our MC/MD method, the original LFMM model is combined with a Monte Carlo scheme based on the Metropolis acceptance/rejection criterion that is used to model spin-crossover transitions in bulk materials with multiple metal centers. We have applied our hybrid MC/MD method to investigate the SCO behavior of {Fe(pz)[Pt(CN) 4 ]}, a prototypical MOF, upon adsorption of various guest molecules. In all cases, excellent agreement was found with the available experimental data, which allowed us to develop a fundamental understanding of the molecular mechanisms that govern spin transitions in MOFs. By correlating molecular-level guest molecule-framework interactions with macroscopic SCO properties, our analysis provides design principles, at the fundamental level, for the development of MOF materials that can efficiently exploit the energy differences between spin states for gas detection and molecular sensing.