Multivariate Anilate-Based Metal–Organic Frameworks: Exploring Assembly and Linker Exchange Pathways

The diverse optical, magnetic, and electronic behaviors of crystalline materials arise from their structure and the nature of their coordination environment. Metal–organic frameworks (MOFs) based on anilate linkers possess rich composition tunability with complex multidimensional architectures, yet multivariate architectures incorporating secondary ligands remain comparatively underinvestigated. Here, we report a comprehensive investigation of the synthetic conditions governing the assembly of multivariate MOFs constructed from anilate and secondary linkers, enabling precise control over their composition and peripheral functionalities. Controlled assembly was achieved by systematically varying synthetic parameters (solvothermal, hydrothermal, and reflux conditions), with particular attention to mild reaction regimes and reaction times to assess their effect on linker incorporation. In addition, post-synthetic linker exchange was explored as a complementary approach to assess the effective tunability of the framework functional properties and to gain insight into coordination dynamics, particularly in how electron-withdrawing substituents modulate exchange efficiency and incorporation patterns. The resulting materials were characterized by single-crystal and powder X-ray diffraction, spectroscopy, and elemental analysis to confirm framework structures, ligand incorporation, and functional integrity. Our findings reveal that careful control of synthetic conditions and post-synthetic linker exchange enables frameworks with predictable multivariate ligand distributions, tunable photophysical properties, and defined coordination dynamics, highlighting design principles for multifunctional MOFs with enhanced compositional and functional control.