Sequential Self-Assembly of Organic Heterostructured Architectures Composed of Low-Dimensional Microcrystals

Organic heterostructured micro-/nanomaterials (OHTMs) integrating heterostructured advantages and organic material character have drawn strong attention in nanoscience and nanotechnology to meet the ever-increasing technological requirements. However, the fine synthesis of OHTMs with high spatial/angular characteristics remains challenging because of the complex epitaxial relationships of material combinations. Herein, we develop a rational sequential self-assembly strategy to synthesize the OHTMs composed of m-BCB or o-BCB one-dimensional (1D) microrods or microbelts as trunks and TPBe 2D microplates as branches via regulating the π–π interaction intensity (|Eo-BCB = −25.56 kcal mol–1| > |Em-BCB = −15.49 kcal mol–1| > |ETPBe = −5.06 kcal mol–1|). Notably, both the lattice matching and the surface–interface energy balance prefer heterogeneous nucleation and epitaxial growth of the branch part on the surfaces of the preformed seed trunk part. Our sequential self-assembly approach demonstrates a universal avenue to precisely synthesize the OHTMs in a desired mode, which provides promising candidate for the integrated optoelectronics.