Side-Chain Tuning of Thermal-Expansion Crossover in Metal-Organic Frameworks

Abstract

Achieving continuous control over macroscopic thermal expansion remains a fundamental challenge in solid-state physics. Using classical and path-integral molecular dynamics alongside lattice dynamics at near-\emph{ab initio} accuracy, we report an entropy-driven thermal-expansion crossover from positive (PTE) to negative thermal expansion (NTE) in alkoxy-functionalized MOF-5, an archetypal metal-organic framework (MOF). We demonstrate that this non-linear response is continuously tunable via the alkoxy side-chain length, quantified by the number of carbon atoms $n$ grafted onto the archetypal cubic MOF-5 framework: systems with short chains ($n \le 2$) exhibit monotonic NTE, whereas longer chains ($n \ge 3$) trigger a pronounced PTE-to-NTE crossover. At low temperatures, thermal activation of longer side chains opens additional conformational states and generates steric pressure inside the pore, driving positive expansion through a gain in side-chain conformational entropy. Conversely, at elevated temperatures, the side chains enhance transverse linker fluctuations and strengthen the string-tension mechanism associated with low-frequency framework modes, causing structural contraction favored by framework vibrational entropy. Finally, by varying the concentration of side-chain-functionalized linkers, the thermal expansion coefficient can be continuously regulated to realize negative, near-zero, and positive thermal expansion within selected temperature windows. These results establish side-chain engineering as a practical route for programming macroscopic thermodynamic responses in MOFs.