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Porous, stacked two-dimensional covalent organic frameworks (2D COFs) bearing semiconducting linkers can support directional charge transfer across adjacent layers of the COF. To better inform the current and possible future design rules for enhancing electron and hole transport in such materials, an understanding of how linker selection and functionalization affects interlayer electronic couplings is essential. We report electronic structure simulation and analysis of electronic couplings across adjacent linker units and to encapsulated species in functionalized electroactive 2D COFs. The detailed dependence of these electronic couplings on interlayer interactions is examined through scans along key interlayer degrees of freedom and through configurational sampling from equilibrium molecular dynamics on semiempirical potential energy surfaces. Beyond affirming the sensitivity of the electronic coupling to interlayer distance and orientation, these studies offer guidance toward linker functionalization strategies for enhancing charge carrier transport in electroactive 2D COFs. 

Solar thermal fuels (STFs) offer a unique way of harnessing energy from the sun by absorbing photons and storing the energy in a metastable photoisomerized state. The reverse isomerization process can then be catalytically or thermally triggered to release the stored energy and return the fuel to its stable configuration. Functionalization of these compounds is necessary to reach practical energy storage densities, but substitutions that increase the energy storage density may adversely impact performance at other steps along the fuel cycle. Recent computational screening efforts to identify high-performance STF candidates have focused on properties that can be estimated from ground-state electronic structure methods. Here we argue that computational screening of STF candidates across the full fuel cycle benefits from a multifactor approach with excited-state properties like excitation energies and photoisomerization quantum yields addressed alongside key ground-state properties like energy storage densities and reverse isomerization barriers. As a critical step toward multifactor high-throughput screening and optimization of STFs, in this work we first systematically simulate the specific storage energy and excitation energy of substituted azobenzene- and norbornadiene-based STFs through electronic structure calculations. Density-functional tight-binding (DFTB) predictions are benchmarked against density functional theory (DFT) and experimental measurements where available. To encompass the complete solar thermal fuel cycle in these compounds, we then apply DFT methods to analyze the reverse isomerization process and its relationship to the photoisomerization quantum yield. We find that DFTB provides a useful balance between accuracy and computational efficiency for virtual screening of STF photoabsorption and energy storage, while isomerization barrier and quantum yield predictions require more sophisticated approaches. 

Abstract Understanding of interactions among molecules is essential to elucidate the binding of pharmaceuticals on receptors, the mechanism of protein folding and self-assembling of organic molecules. While interactions between two aromatic molecules have been examined extensively, little is known about the interactions between two antiaromatic molecules. Theoretical investigations have predicted that antiaromatic molecules should be stabilized when they stack with each other by attractive intermolecular interactions. Here, we report the synthesis of a cyclophane, in which two antiaromatic porphyrin moieties adopt a stacked face-to-face geometry with a distance shorter than the sum of the van der Waals radii of the atoms involved. The aromaticity in this cyclophane has been examined experimentally and theoretically. This cyclophane exhibits three-dimensional spatial current channels between the two subunits, which corroborates the existence of attractive interactions between two antiaromatic π-systems. 

Abstract A three‐component synthesis methodology is described for the formation of covalent organic frameworks (COFs) containing extended aromatics. Notably, this approach enables synthesis of the building blocks and COF along parallel reaction landscapes, on a similar timeframe. The use of fragmental building block components, namely pyrene dione diboronic acid as aggregation‐inducing COF precursor and the diamineso‐phenylenediamine (Ph), 2,3‐diaminonaphthalene (Naph), or (1R,2R)‐(+)‐1,2‐diphenylethylenediamine (2Ph) as extending functionalization units in conjunction with 2,3,6,7,10,11‐hexahydroxytriphenylene, resulted in the formation of the corresponding pyrene‐fused azaacene, i.e., Aza‐COF series with full conversion of the dione moiety, long‐range order, and high surface area. In addition, the novel three‐component synthesis was successfully applied to produce highly crystalline, oriented thin films of the Aza‐COFs with nanostructured surfaces on various substrates. The Aza‐COFs exhibit light absorption maxima in the blue spectral region, and each Aza‐COF presents a distinct photoluminescence profile. Transient absorption measurements of Aza‐Ph‐ and Aza‐Naph‐COFs suggest ultrafast relaxation dynamics of excited‐states within these COFs.