Tuning Thermal Expansion in Metal-Organic Frameworks Using a Mixed Linker Solid Solution Approach

Samuel J Baxter; Andreas Schneemann; Austin D Ready; Pavithra Wijeratne; Angus P Wilkinson; Nicholas C Burtch

doi:10.1021/jacs.9b06109

Tuning Thermal Expansion in Metal-Organic Frameworks Using a Mixed Linker Solid Solution Approach

J Am Chem Soc. 2019 Aug 14;141(32):12849-12854. doi: 10.1021/jacs.9b06109. Epub 2019 Jul 31.

Authors

Samuel J Baxter¹, Andreas Schneemann¹, Austin D Ready¹, Pavithra Wijeratne¹, Angus P Wilkinson, Nicholas C Burtch¹

Affiliation

¹ Sandia National Laboratory , Livermore , California 94550 , United States.

PMID: 31319663
DOI: 10.1021/jacs.9b06109

Abstract

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-TM_x, 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.