Mapping Solvation Environments in Porous Metal-Organic Frameworks with Infrared Chemical Imaging

We report here the first mesoscale characterization of solvent environments in the metal-organic framework (MOF) Cu₃(BTC)₂ using infrared imaging. Two characteristic populations of the MOF structures corresponding to the carboxylate binding to the Cu(II) (metal) ions were observed, which reflect a regular solvated MOF structure with axial solvents in the binuclear copper paddlewheel and an unsolvated defect mode that lacks axial solvent coordination. Infrared imaging also shows strong correlation between solvent localization and the spatial distribution of the solvated population within the MOF. This is a vital result as any remnant solvent molecules adsorbed inside of MOFs can render them less effective. We propose fast IR imaging as a potential characterization technique that can measure adsorbate and defect distributions in MOFs.