Dibenzochrysene enables tightly controlled docking and stabilizes photoexcited states in dual-pore covalent organic frameworks

Abstract

Covalent organic frameworks (COFs), consisting of covalently connected organic building units, combine attractive features such as crystallinity, open porosity and widely tunable physical properties.

Quantifying the Likelihood of Structural Models through a Dynamically Enhanced Powder X‐Ray Diffraction Protocol

“…Similar to the chosen 3D COFs, COF‐5 was one of the first ever synthesized COFs, [10] adopting the hcb topology. TP‐COF [49, 50] was chosen as an isoreticularly expanded equivalent of COF‐5, whereas TA DBC‐COF [51] was chosen due to its unique kgm topology.…”

“… TA DBC‐COF model refinement for three distinct structural models with the kgm topology but varying orientation of the imine linkage and hence varying embedding, resulting in a different pore geometry and PXRD heuristic value. The PXRD patterns are obtained experimentally [51] (gray, background‐filtered) or through our dynamic approach (colored).…”

“…Forschungsartikel building blocks were chosen based on their varying sizes, symmetries and connectivities.T he two 3D COFs,C OF-103 and COF-108, were among the first 3D COFs to have ever been synthesized [48] and exhibit the ctn and bor topology, respectively.T he bottom panel shows the three 2D COFs. Similar to the chosen 3D COFs,C OF-5 was one of the first ever synthesized COFs, [10] adopting the hcb topology.T P-COF [49,50] was chosen as an isoreticularly expanded equivalent of COF-5, whereas TA DBC-COF [51] was chosen due to its unique kgm topology.…”

Quantifying the Likelihood of Structural Models through a Dynamically Enhanced Powder X‐Ray Diffraction Protocol

“…building blocks were chosen based on their varying sizes, symmetries and connectivities.T he two 3D COFs,C OF-103 and COF-108, were among the first 3D COFs to have ever been synthesized [48] and exhibit the ctn and bor topology, respectively.T he bottom panel shows the three 2D COFs. Similar to the chosen 3D COFs,C OF-5 was one of the first ever synthesized COFs, [10] adopting the hcb topology.T P-COF [49,50] was chosen as an isoreticularly expanded equivalent of COF-5, whereas TA DBC-COF [51] was chosen due to its unique kgm topology.…”

Structural Approaches to Control Interlayer Interactions in 2D Covalent Organic Frameworks

“…Bein and co‐workers have also reported the synthesis of DBC‐based 2D COFs through the direct condensation of dibenzo[ g,p ]chrysene‐2,7,10,15‐tetraamine (DBCTA, Figure 7). [ 49 ] Its condensation with linear dialdehydes, such as terephthalaldehyde, 4,4′‐biphenyldicarbaldehyde and thieno[3,2‐ b ]thiophene‐2,5‐dicarboxaldehyde, led to highly crystalline imine‐linked COFs (DBC–COFs) with hexagonally faceted single crystals ranging from 50 to 150 nm. The reduced torsion of the dibenzochrysene monomer produced an interlayer stacking distance of ≈3.6 Å, which was ≈1 Å shorter than in 2D COFs derived from ETTA.…”