Electronic circular dichroism is an important optical phenomenon offering insights into chiral molecular materials. On the other hand, metal–organic frameworks (MOFs) are a novel group of crystalline porous thin‐film materials that provide tailor‐made chemical and physical properties by carefully selecting their building units. Combining these two aspects of contemporary material research and integrating chiral molecules into MOFs promises devices with unprecedented functionality. However, considering the nearly unlimited degrees of freedom concerning the choice of materials and the geometrical details of the possibly structured films, urgently it needs to complement advanced experimental methods with equally strong modeling techniques. Most notably, these modeling techniques must cope with the challenge that the material and devices thereof cover size scales from Ångströms to mm. In response to that need, a computational workflow is outlined that seamlessly combines quantum chemical methods to capture the properties of individual molecules with optical simulations to capture the properties of functional devices made from these molecular materials. The focus is on chiral properties and applying work to UiO‐67‐BINOL MOFs, for which experimental results are available to benchmark the results of the simulations and explore the optical properties of cavities and metasurfaces made from that chiral material.
New single‐site catalysts based on mixed‐linker metal‐organic frameworks with DUT‐5 structure, which contain immobilized Co2+, Mn2+ and Mn3+ complexes, have successfully been synthesized via post‐synthetic modification. 2,2’‐Bipyridine‐5,5’‐dicarboxylate linkers were directly metalated, while 2‐amino‐4,4’‐biphenyldicarboxylate linkers were post‐synthetically modified by their conversion to Schiff‐base ligands and a subsequent immobilization of the metal complexes. The resulting materials were used as catalysts in the selective epoxidation of trans‐stilbene and the activities and selectivities of the different catalysts were compared. The influence of various reaction parameters on conversion, yield and selectivity were investigated. Very low catalyst amounts of 0.02 mol % were sufficient to obtain a high conversion of trans‐stilbene using molecular oxygen from air as the oxidant. For cobalt‐containing MOF catalysts, conversions up to 90 % were observed and, thus, they were more active than their manganese‐containing counterparts. Recycling experiments and hot filtration tests proved that the reactions were mainly catalyzed via heterogeneous pathways.
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