Metal-organic frameworks (MOFs) are porous, crystalline solids that can be formed in a controlled manner through judicious choice of metal ions and organic linker molecules. Luminescent metal-organic frameworks (LMOFs) can derive their emissive nature from certain properties of the metal ions or linkers. Additionally, LMOFs can be created by incorporating a luminescent transition metal complex (TMC) into the framework structure via the organic ligands on the transition metal complex. The LMOF should retain the luminescent properties of the transition metal complex and allow for interactions between analytes of interest and TMC within the pores of the MOF. In this study the MOF, Zn3(bpdc)6(bpy) (where bpdc = biphenyldicarboxylate and bpy = 4,4’-bipyridine) is doped with small amounts of [Os(CO)2Cl2(dcphen)] (where dcphen = 4,7-dicarboxylate-1,10-phenanthroline). This complex exhibits large dipole moments within the excited state which results in significant luminescence anisotropy. Upon incorporation of the osmium complex into the LMOF, emission from an MLCT excited state is observed around 590 nm. Uptake of a variety of small molecules of varying polarity has little impact on this emission. However, when small alcohols are incorporate into the pores of the LMOF, the MLCT-based emission is not observed. It is proposed that a lack of solvation of the osmium complex due to strong solvent-solvent interactions within the LMOF pore prevents population of the MLCT excited state, accounting for the lack of emission. The osmium complex has been utilized in other MOF systems to probe this unique behavior in the presence of alcohols.

Emission dependence on guest molecule structure in luminescent metal-organic frameworks doped with polypyridyl osmium complexes

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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