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Double‐bond photoswitching molecules typically can undergo trans→cis photoisomerization, but their photoisomerization mechanisms in the solid state have been rarely reported. Herein, the excited‐state evolutions of trans‐azobenzene (AB), trans‐stilbene (TS), and N‐benzylideneaniline (NBA) are studied to unveil the relationship between the double‐bond photoswitching molecules and the photoisomerization kinetics in the solution phase and in nanocrystal suspensions (NCS). The photoisomerization rate of NBA is the fastest among these three molecules in the solution phase due to its most apparent single‐bond feature of the central double bond in the S1 state. The free space ordered crystal configuration boosts the photoisomerization rates of AB and TS in NCS to be faster than that of the solution phase because the hindrance of the wrapping solvent is eliminated in the crystals. In contrast, when NBA is prepared into NCS, it becomes distorted into a nonplanar structure because of the asymmetrical C‐H···π interactions, resulting in NBA having a large spin‐orbital coupling (SOC) value which opens the intersystem crossing channel to generate the triplet state instead of undergoing photoisomerization in solution. Therefore, this work reveals that the crystal configuration and the molecular structure may critically determine the photophysical properties of photoswitching materials. [ABSTRACT FROM AUTHOR]

Long persistent luminescence (LPL) can store light energy in excited states and gradually release it as light. Organic host–guest systems provide a good platform for LPL, and single‐color LPL is often achieved while multicolor LPL is challengeable. Here host–guest supramolecular complexes are presented with dual LPL emissions: thermally activated delayed fluorescence (TADF) (≥100 ms) and room temperature phosphorescence (RTP). A space charge transfer from α‐cyclodextrin to diphenylacetylene (DPA) with long‐range transportation (2.32 mm) carrier along DPA strand in the supramolecular complexes is attributed to generate the TADF and RTP. Fortunately, these supramolecular complexes are readily fabricated from α‐cyclodextrin and DPA or DPA derivatives. The gradient color is observed after removing UV excitation. Furthermore, the hydrophobic property inside α‐cyclodextrin makes the LPL appear by water shedding and disappear by organic solvent infiltration, showing the character of a "switch." This host–guest space charge transfer strategy paves a way to design LPL materials. [ABSTRACT FROM AUTHOR]

Host-guest supramolecules, room temperature phosphorescence, space charge transfer, thermally activated delayed fluorescence, ultrafast spectroscopy Keywords: host-guest supramolecules; room temperature phosphorescence; space charge transfer; thermally activated delayed fluorescence; ultrafast spectroscopy EN host-guest supramolecules room temperature phosphorescence space charge transfer thermally activated delayed fluorescence ultrafast spectroscopy 1 1 1 12/22/21 20211217 NES 211217 A novel supramolecular complex composed of diphenylacetylene (DPA) and -cyclodextrin ( -CD) with dual ultralong thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP) is reported by Ming-De Li and co-workers in article number 2101337. The space charge transfer from host to guest and a long-range charge transportation are responsibe for the unprecedented optical property. [Extracted from the article]