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

2025/09/09 by Patrick Lechner, G. Ganguly, Michael J. Sahre +3 · 1 voice
Chemistry · Materials Science · Physics and Astronomy · #Advanced Condensed Matter Physics #Magnetism in coordination complexes #Metal-Organic Frameworks: Synthesis and Applications

paper · pdf · doi:10.1002/anie.202514014

openalex publication_date 2025/09/09 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

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 ‐O) nodes. Using flip‐spin, broken‐symmetry DFT, we identify the true ground state as an antiferromagnetic 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 and CO binding. Spin frustration enhances fixation at room temperature, while its loss upon partial reduction suppresses this activity but promotes CO adsorption via ‐backbonding. These findings challenge current computational conventions and highlight spin frustration as a critical electronic feature in these frameworks.

Citations

• Effect of the damping function in dispersion corrected density functional theory
• Quantum Spin Liquids
• The Current Status of MOF and COF Applications
• Software update: The ORCA program system—Version 5.0
• Energies, structures, and electronic properties of molecules in solution with the C‐PCM solvation model

Discussions

• Lead author Patrick Lechner starts his PhD with a "Very Important Paper" in Angewandte Chemie! doi.org/10.1002/anie... His simulations reveal how spin frustration is key to understanding iron-based MO [bsky, 1 points, 0 comments]

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