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In this contribution, we describe a library of nine different molecular asterisks, all based on aromatic thioethers. Here, the substitution patterns of the central core unit bearing two nitriles and the rotors featuring methoxy groups were permuted. In addition, the photophysical properties in the solid and aggregated state were investigated. X‐ray diffractometry confirmed the molecular structures. In this frame, the molecular packing in the crystal lattice of the two polymorphs of mNoM was extensively studied and a correlation between photoluminescence and secondary interactions was evaluated. In the solid state, all compounds showed emission in the yellow to red part of the electromagnetic spectrum (555–644 nm) with lifetimes of up to 25 μs and photoluminescence quantum yields of up to 47 %, depending on the substitution pattern. As all the evaluated compounds perform as good emitters with aggregation‐induced phosphorescence (AIP), these compounds can be regarded as multivalent platforms for future applications in supramolecular assemblies or as biomedical labels due to the versatile substitution patterns, manifold geometries as well as appealing photophysical properties. [ABSTRACT FROM AUTHOR]

We mapped the entire visible range of the electromagnetic spectrum and achieved white light emission (CIE: 0.31, 0.34) by combining the intrinsic ns‐fluorescence with ultralong ms‐phosphorescence from purely organic dual emitters. We realized small molecular materials showing high photoluminescence quantum yields (ΦL) in the solid state at room temperature, achieved by active exploration of the regioisomeric substitution space. Chromophore stacking‐supported stabilization of triplet excitons with assistance from enhanced intersystem crossing channels in the crystalline state played the primary role for the ultra‐long phosphorescence. This strategy covers the entire visible spectrum, based on organic phosphorescent emitters with versatile regioisomeric substitution patterns, and provides a single molecular source of white light with long lifetime (up to 163.5 ms) for the phosphorescent component, and high overall photoluminescence quantum yields (up to ΦL=20 %). [ABSTRACT FROM AUTHOR]