| Abstract: | Mechanoluminescence (ML) and room‐temperature photophosphorescence (RTP) were achieved in polymorphisms of a triphenylamine derivative with ortho‐substitution. This molecular packing‐dependent emission afforded crucial information to deeply understand the intrinsic mechanism of different emission forms and the possible packing–function relationship. With the incorporation of solid‐state 13C NMR spectra of single crystals, as well as the analysis of crystal structures, the preferred packing modes for ML and/or RTP were investigated in detail, which can guide the reasonable design of organic molecules with special light‐emission properties. |
