Linker Expansion and Its Impact on Switchability in Pillared-Layer MOFs.

Linker elongation is an important method to systematically adjust porosity and pore size in isoreticular MOFs. In flexible structures, this approach opens the possibility for the systematic analysis of the building blocks and their contribution to the overall flexible behavior enabling tuning of the framework responsivity toward molecular stimuli. In this work, we report two new compounds isoreticular to the highly flexible pillared layer structure DUT-8(Ni) ([Ni(2,6-ndc)(dabco)], 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicylo[2.2.2]octane). Aromatic linker 2,6-ndc was substituted by longer carboxylic linkers, namely, 4,4'-biphenyldicarboxylate (4,4'-bpdc) and 4,4'-stilbenedicarboxylate (4,4'-sdc), while the dabco pillar was retained. The structural response of the new compounds toward the desolvation and adsorption of various fluids was studied using advanced in situ PXRD techniques, demonstrating distinct differences in the flexible behavior of three compounds and disclosing the impact of linker structure on the framework response. Theoretical calculations provide mechanistic insights and an energetic rationale for the pronounced differences in switchability observed. The energetics of linker bending and linker-linker dispersion interactions govern the phase transitions in investigated MOFs.