Conversion of Flexible Spin Crossover Metal–Organic Frameworks Macrocrystals to Nanocrystals Using Ultrasound Energy: A Study on Structural Integrity by MicroED and Charge‐Transport Properties

Abstract Metal–Organic Frameworks (MOFs) attract attention for their intrinsic porosity, large surface area, and functional versatility. To fully utilize their potential in applications requiring precise control at smaller scales, it is essential to overcome challenges associated with their bulk form. This is particularly difficult for 3D MOFs with spin crossover (SCO) behavior, which undergo a reversible transition between high‐spin and low‐spin states in response to external stimuli. Maintaining their structural integrity and SCO properties at the nanoscale remains a significant challenge, yet these properties make them ideal candidates for sensors, data storage, and molecular switch applications. This study reports the synthesis of nanocrystals of the well‐known SCO MOF [Fe ₂ (H _0.67 bdt) ₃ ]·xH ₂ O ( 1 , x = 0–10, bdt ²⁻ = 1,4‐benzeneditetrazolate), which exhibits both magnetic and charge transport properties. The nanocrystals are obtained through sonication of macrocrystals, and the preservation of their crystalline structure at the nanoscale is explored using Microcrystal Electron Diffraction (MicroED). A comparison between macro‐ and nanocrystals highlights the structural integrity and the preservation of charge‐transport properties, underlining the potential for further miniaturization of MOFs for advanced technological applications.