Spin Frustration Determines the Stability and Reactivity of Metal-Organic Frameworks with Triangular Iron(III)-Oxo Clusters.

ABSTRACT: Density functional theory (DFT) is the standard approach for modeling MIL-101(Fe) and related Fe-based metal-organic frameworks, typically assuming a ferromagnetic high-spin configuration. However, this widely adopted approach overlooks a key electronic feature: Spin frustration in the triangular Fe3(μ3${\rm Fe}_{3}(\mu _{3}$ -O) nodes. Using flip-spin, broken-symmetry DFT, we identify the true ground state as an antiferromagnetic 2S+1=6$2S+1=6$ state that standard DFT fails to capture. We demonstrate that neglecting spin frustration in MIL-101(Fe) leads to structural distortions, incorrect energetics, and misleading predictions of stability and reactivity. By explicitly accounting for spin frustration, we recover the correct structure and rationalize the temperature-dependent N2${\rm N}_{

SUBMITTER: Lechner P 

PROVIDER: S-EPMC12501687 | biostudies-literature | 2025 Oct

REPOSITORIES: biostudies-literature