Nucleation Control-Triggering Cocrystal Polymorphism of Charge-Transfer Complexes Differing in Physical and Electronic Properties
Jianqun Jin, Shanyu Wu, Yu-Dong Ma, C. Dong, Wei Wang, Xitong Liu, Haixiao Xu, Guankui Long, Mingtao Zhang, Jing Zhang, Wei Huang
Abstract
']-dithiophene (DTTCNQ) were synthesized separately via a simple artificial nucleation-tailoring method, in both macroscopic and microscopic cocrystal engineering manners. The two polymorphs were testified to be independently thermosalient in the solid state, and the specific self-assembly derived from homogeneous or heterogeneous nucleation by assistance of governable thermodynamic/kinetic drive, leading to a change in the ordered p-n stacking structure. The as-prepared polymorphic microcrystals afforded a significantly varied (opto)electronic property: high n-type transporting and good photoresponsivity for β-complex, and ambipolar transporting with ignorable photoresponsivity for α-complex, attributing to the different charge-transfer and supramolecular alignment. This work provides us a new route to the exploitation of donor-acceptor complex family, making it possible to develop functional materials and devices based on variable supramolecular binary structures.