Optoelectronic material properties are governed by the whole collective of organic moieties, and these aggregate states present the characteristic performance of extended assemblies with different molecular packing, not only of single molecules themselves. Thus, controlling molecular packing is an essential issue for obtaining the optimized optical and electronic properties. It is also a great challenge because of the unclear structures and complicated intermolecular interactions, including dispersion forces, electrostatic interactions and hydrogen bonding. Moreover, upon the introduction of some external force as the stimulus source, dynamic optical properties can be achieved with the transformation of molecular packing in some cases, such as the photoinduced room temperature phosphorescence (RTP) effect, mechanochromic luminescence, the thermal treatment-dependent mechanoluminescence effect, and the optimized nonlinear optical (NLO) property achieved after electric poling. Therefore, it is essential to understand the relation between characteristics of molecular packing and the resultant optoelectronic performance at the molecular level, which becomes increasingly demanding for the further development of functional materials for their applications in organic light-emitting diodes (OLEDs), chemo- and biosensors, organic solar cells, data storage, and anticounterfeiting devices.

This Account gives a summary of our research on the molecular design of optoelectronic materials, with the consideration of a molecular uniting effect in different aggregated states, such as crystalline states, thin films, and nanoparticles. Through the systematical investigation of structure–packing–performance relationships, some strategies are afforded to partially control the molecular packing via the tunable size, shape, and configuration of aromatic moieties with different electronic and steric effects, together with different types of substituents as functional units to adjust the intermolecular interactions. The utilization of π–π interactions and hydrogen bonding by rational molecular design is considered as the key point to achieve the bright emission of organic materials, including the RTP and mechanoluminescence effects. Also, the dynamic optoelectronic properties are highlighted with different kinds of stimuli, including light irradiation, mechanical force, thermal treatment, and electric field, which are mainly related to the subtle molecular motions under external force and the changeable molecular packing as the metastable state. These selected examples will not only open a window for further development of organic and polymeric optoelectronic materials by the adjustable molecular packing and noncovalent interactions, but also prompt further advances for more interesting and exciting properties.