To optimize the optical and optoelectronic functionalities of two-dimensional (2D) covalent organic frameworks (COFs), detailed properties of emissive and nonradiative pathways after photoexcitation need to be elucidated and linked to particular structural designs. Here, we use transient absorption (TA) spectroscopy to study the colloidal suspension of the full sp2carbon-conjugated sp2c-COF and characterize the spatial extent and diffusion dynamics of the emissive excitons generated by impulsive photoexcitation. The ∼3.5 Å stacking distance between 2D layers results in cofacial pyrene excitons that diffuse through the framework, while the state that dominates the emissive spectrum of the polycrystalline solid is assigned to an extended cofacial exciton whose 2D delocalization is promoted by C═C linkages. The subnanosecond kinetics of a photoinduced absorption (PIA) signal in the near-infrared, attributed to a charge-separated exciton, or polaron pair, reflects three-dimensional (3D) exciton diffusion as well as long-range exciton-exciton annihilation driven by resonance interactions. Within our experimental regime, doubling the excitation intensity results in a 10-fold increase in the estimated exciton diffusion length, from ∼3 to ∼30 nm, suggesting that higher lattice temperature may enhance exciton mobility in the COF colloid.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry