In Situ Probe Supramolecular Self-Assembly Dynamics and Chirality Transfer Mechanism at Air–Water Interface

Hierarchically Organized Cocrystal of Tetra‐Anionic Porphyrin and Di‐Cationic Viologen: Ion Conformations, Supramolecule Interactions, and Porphyrin Arrays

“…The size of crystal can be adjusted by controlling the temperature and wind speed of blowing in electrothermal blowing dry box. The quick growth of crystal size is distinct from that reported in previous studies because the co‐assembly architectures of tetra‐anionic porphyrins were difficult to grow to a suitably large size for SCXRD [19–30] . The rapid growth in crystal size can be attributed to the reasonable selection of counterion ligand and co‐assembly method.…”

“…Herein, a hierarchically ordered ionic cocrystal of meso‐tetra(4‐sulfonatophenyl)‐porphyrin (TSPP 4− ) and N , N ′‐diethyl viologen (DEV 2+ ) is reported, wherein wave‐like and saddle‐like TSPP 4− ions co‐aggregate at a stoichiometric ratio of 1 : 2 to form unique J‐type porphyrin arrays. The rapid growth in crystal size is distinct from that reported in previous studies because the co‐assembly architectures of tetra‐anionic porphyrins were difficult to grow to a suitably large size for SCXRD [19–30] . The diversity of ionic conformations in the crystal leads to intricate supramolecular interactions.…”

“…Therefore, hierarchical co‐assembly of ionic porphyrins can be used to create materials with potential application value in organic semiconductors and sunlight catalysts. In the past decade, research on the hierarchically organized architectures of tetra‐ionic porphyrins focused on two types of properties, namely, chirality transfer and sunlight catalysis [18‐27] . Non‐chiral tetra‐ionic porphyrins co‐assemble with chiral organic ions, endowing chirality to the assembled structures, which exhibit chirality signal in the absorption and emission spectrum of tetra‐ionic porphyrins [19‐23] .…”

“…Different morphologies, such as micro‐sphere, nano‐rod, nano‐belt, nano‐flower, nano‐sheet, and double helix, of architectures were obtained by the hierarchical co‐assembly of tetra‐ionic porphyrins [19–29] . Researchers have generally speculated the aggregate style of tetra‐ionic‐porphyrins in co‐assembled architectures by contrasting UV‐vis spectra of the co‐assembled architectures and tetra‐ionic porphyrins in dilute solution.…”

“…Researchers have generally speculated the aggregate style of tetra‐ionic‐porphyrins in co‐assembled architectures by contrasting UV‐vis spectra of the co‐assembled architectures and tetra‐ionic porphyrins in dilute solution. The blueshift or redshift in the spectra of co‐assembled architectures, compared with that of the dilute solution, indicate the existence of H‐/J‐aggregates of tetra‐ionic porphyrins in the co‐assembled architectures; and manty tetra‐ionic porphyrins aggregates in these architectures are bridged by counterion ligands [19–29] . Because the hierarchical co‐assembled architectures of tetra‐ionic porphyrins usually are difficult to grow to a size suitable for single‐crystal X‐ray diffraction (SCXRD), the single‐crystal structures of these architectures were rarely reported.…”