Control over Kinetic and Thermodynamically Driven Pathways of Crystallization to Yield Cofacial and Slipped‐Stack Dimers in Single Crystals

Control over the molecular packing in the solid state is of utmost importance in regulating the bulk optical properties of organic semiconductors. The electronic coupling between the molecules makes it possible to improve the properties of the bulk materials. This work reports an example of control over the selective formation of polymorphic single crystals of donor–acceptor‐type small‐molecule compound 25TR by 1) kinetic or 2) thermodynamic course of crystallisation to yield slipped stack (S) and cofacial (C) dimers in the single crystals. The distinct optical characteristics of the C‐dimer and S‐dimer are summarised. Both forms show significant excitonic interactions in the solid state, and the S‐dimeric form has strong yellowish orange fluorescence, whereas the C‐dimeric form is non‐fluorescent in the crystalline state. DFT calculations and differential scanning calorimetric experiments revealed that the C‐dimer polymorph is the thermodynamically stable form with a free energy offset of 0.43 eV in comparison with the S‐dimer. Interestingly, the thermodynamically driven non‐fluorescent single crystal was found to be convertible to its fluorescent form irreversibly by thermal trigger. The charge‐carrier‐transport characteristics of these two polymorphs were computed by using the Marcus–Hush formalism. The computations of the charge‐carrier‐transport behaviour revealed that the S‐dimer (25TR(R)) is ambipolar, whereas the C‐dimer (25TR(Y)) is predominantly n‐type. Total control: Control over both thermodynamic and kinetic courses of crystallization to acquire cofacial or slipped‐stack type molecular dimers having distinct optical and charge‐carrier transport properties in single crystals of a donor–acceptor‐type small‐molecule compound is reported. The thermodynamically driven non‐fluorescent single‐crystalline form can be converted to the kinetically driven fluorescent polymorph by thermal annealing.