What Leads to Aggregation-Induced Emission?

Aggregation-induced emission (AIE), usually referring to the phenomenon in which molecules emit more strongly in the aggregate state than in the solution state, is intriguing and promising in various optoelectronic and biosensing applications. In this Perspective, the basic principles that can lead to AIE and experimental evidence to reveal the AIE mechanism of tetraphenyl ethylene (TPE)-type molecules are discussed. AIE is the consequence of two factors: (1) the fast energy dissipation by crossing a conical intersection (CI) in solutions but not in solids results in low luminescence efficiencies in the solutions, and (2) the weak intermolecular coupling and thus slow intermolecular energy/charge transfers in the AIE solids effectively prevent quenching and result in relatively high luminescence efficiencies. The key to AIE is that the luminescence efficiency is tuned by controlling molecules to cross or not to cross a CI by changing the phase of molecules. How fast a molecule can cross a CI is dependent on the energy barrier of isomerization, which can be tuned in many ways, including mechanical or electrical stimuli, in addition to changing phases. Barrier-dependent crossing CI also results in a very important consequence: excitation-wavelength-dependent fluorescence yield within one electronic excited state, an anti-Vavilov’s rule phenomenon. In principle, there can be an alternative way to tune luminescence efficiency by manipulating the formation of CIs instead of crossing or not crossing them. This approach relies on the fact that the electronic ground state and the excited state have many different properties, e.g., dipole moment. By tuning the environment, e.g., dielectric constant, to favor or disfavor one state, one may be able to lift or lower the potential surface of one state so that the potential surfaces of two states can vary between intersected and not contacted.