Excited-State Electronic Properties in Zr-Based Metal–Organic Frameworks as a Function of a Topological Network

Molecular assemblies in metal–organic frameworks (MOFs) are reminiscent of natural light-harvesting (LH) systems and considered as emerging materials for energy conversion. Such applications require understanding the correlation between their excited-state properties and underlying topological net. Two chemically identical but topologically different tetraphenylpyrene (1,3,6,8-tetrakis( p -benzoicacid)pyrene; H 4 TBAPy)-based Zr IV MOFs, NU-901 ( scu ) and NU-1000 ( csq ), are chosen to computationally and spectroscopically interrogate the impact of topological difference on their excited-state electronic structures. Time-dependent density functional theory-computed transition density matrices for selected model compounds reveal that the optically relevant S 1, S 2, and S n states are delocalized over more than four TBAPy linkers with a maximum exciton size of ∼1.7 nm (i.e., two neighboring TBAPy linkers). Computational data further suggests the evolution of polar excitons (hole and electron residing in two different linkers); their oscillator strengths vary with the extent of interchromophoric interaction depending on their topological network. Femtosecond transient absorption (fs-TA) spectroscopic data of NU-901 highlight instantaneous spectral evolution of an intense S 1 → S n transition at 750 nm, which diminishes with the emergence of a broad (580–1100 nm) induced absorption originating from a fast excimer formation. Although these ultrafast spectroscopic data reveal the first direct spectral observation of fast excimer formation (τ = 2 ps) in MOFs, the fs-TA features seen in NU-901 are clearly absent in NU-1000 and the free H 4 TBAPy linker. Furthermore, transient and steady-state fluorescence data collected as a function of solvent dielectrics reveal that the emissive states in both MOF samples are electronically nonpolar; however, low-lying polar excited states may get involved in the excited-state decay processes in polar solvents. The present work shows that the topological arrangement of the linkers critically controls the excited-state electronic structures.