Guest-Dependent Stabilization of the Low-Spin State
in Spin-Crossover Metal-Organic
Frameworks
- Publication date
- Publisher
Abstract
Computer simulations
are carried out to characterize the variation
of spin-crossover (SCO) behavior of the prototypical {Fe(pz)[Pt(CN)<sub>4</sub>]} metal-organic framework (MOF) upon adsorption of chemically
and structurally different guest molecules. A detailed analysis of
both strength and anisotropy of guest molecule–framework interactions
reveals direct correlations between the mobility of the guest molecules
inside the MOF pores, the rotational mobility of the pyrazine rings
of the framework, and the stabilization of the low-spin state of the
material. On the basis of these correlations, precise molecular criteria
are established for predicting the spin state of {Fe(pz)[Pt(CN)<sub>4</sub>]} upon guest adsorption. Finally, predictions of the SCO
temperature upon adsorption of various toxic gases demonstrate that
in silico modeling can provide fundamental insights and design principles
for the development of spin-crossover MOFs for applications in gas
detection and chemical sensing