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Updated: Dec 7, 2025
Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks
Published on: February 10, 2023
Crystalline assembly of perylene in metal-organic framework thin film: J-aggregate or excimer? Insight into the
Mariana Kozlowska1, Yohanes Pramudya1, Marius Jakoby2
1Karlsruhe Institute of Technology, Institute of Nanotechnology, Hermann-von-Helmholtz Platz-1, 76344 Eggenstein-Leopoldshafen, Germany.
Abstract:
The spatial orientation of chromophores defines the photophysical and optoelectronic properties of a material and serves as the main tunable parameter for tailoring functionality. Controlled assembly for achieving a predefined spatial orientation of chromophores is rather challenging. Metal-organic frameworks (MOFs) are an attractive platform for exploring the virtually unlimited chemical space of organic components and their self-assembly for device optimization. Here, we demonstrate the impact of interchromophore interactions on the photophysical properties of a surface-anchored MOF (SURMOF) based on 3,9-perylenedicarboxylicacid linkers. We predict the structural assembly of the perylene molecules in the MOF via robust periodic density functional theory calculations and discuss the impact of unit topology and π-π interaction patterns on spectroscopic and semiconducting properties of the MOF films. We explain the dual nature of excited states in the perylene MOF, where strong temperature-modulated excimer emission, enhanced by the formation of perylene J-aggregates, and low stable monomer emission are observed. We use band-like and hopping transport mechanisms to predict semiconducting properties of perylene SURMOF-2 films as a function of inter-linker interactions, demonstrating both p-type and n-type conduction mechanisms. Hole carrier mobility up to 7.34 cm2Vs-1is predicted for the perylene SURMOF-2. The results show a promising pathway towards controlling excimer photophysics in a MOF while controlling charge carrier mobility on the basis of a predictive model.
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