Tuning Thermal Expansion in Metal–Organic Frameworks Using a Mixed Linker Solid Solution Approach
2019
Baxter, Samuel J. | Schneemann, Andreas | Ready, Austin D. | Wijeratne, Pavithra | Wilkinson, Angus P. | Burtch, Nicholas C.
Several metal–organic frameworks are known to display negative thermal expansion (NTE). However, unlike traditional NTE material classes, there have been no reports where the thermal expansion of a MOF has been tuned continuously from negative to positive through the formation of single-phase solid solutions. In the system Zn-DMOF-TMₓ, Zn₂[(bdc)₂–₂ₓ(TM-bdabco)₂ₓ][dabco], the introduction of increasing amounts of TM-bdc, with four methyl groups decorating the benzene dicarboxylate linker, leads to a smooth transition from negative to positive thermal expansion in the a–b plane of this tetragonal material. The temperature at which zero thermal expansion occurs evolves from ∼186 K for the Zn-DMOF parent structure (x = 0) to ∼325 K for Zn-DMOF-TM (x = 1.0). The formation of mixed linker solid solutions is likely a general strategy for the control of thermal expansion in MOFs.
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