Design of Highly Photofunctional Porous Polymer Films with Controlled Thickness and Prominent Microporosity

Abstract

Porous organic polymers allow the integration of various π-units into robust porous π-networks, but they are usually synthesized as unprocessable solids with poor light-emitting performance as a result of aggregation-related excitation dissipation. Herein, we report a general strategy for the synthesis of highly emissive photofunctional porous polymer films on the basis of a complementary scheme for the structural design of aggregation-induced-emissive π-systems. We developed a high-throughput and facile method for the direct synthesis of large-area porous thin films at the liquid–electrode interface. The approach enables the preparation of microporous films within only a few seconds or minutes and allows precise control over their thickness with sub-nanometer precision. By virtue of rapid photoinduced electron transfer, the thin films can detect explosives with enhanced sensitivity to low parts-per-million levels in a selective manner.

Turn‐On Fluorescence in Tetra‐NHC Ligands by Rigidification through Metal Complexation: An Alternative to Aggregation‐Induced Emission

“…Fore xample,i tw as demonstrated that high fluorescence quantum yields can be achieved upon rigidifying TPE-based species within metal-organic frameworks (MOFs). [14] Anion coordination to an oligourea-functionalized TPE derivative even gave a F F value as high as 41.3 %in concentrated solutions. [1e] Theintramolecular rotation of TPE has also been locked inside porous organic polymers to obtain an enhanced fluorescence quantum yield (F F )of40% in the solid state.…”

Luminescent Porous Polymers Based on Aggregation‐Induced Mechanism: Design, Synthesis and Functions

“…Porous organic polymers (POPs) are a unique class of amorphous porous polymers that combine covalent π‐networks with inherent porosity. POPs are a class of emerging multifunctional materials and show outstanding properties and functions in various applications, such as gas storage, light emitting, catalysis, energy transfer and energy storage . They are robust in stability as a result of strong covalent bond‐linked network structure and can be synthesized using a variety of different π‐units.…”

“…Although various π‐units have been utilized as monomers for the synthesis of π‐electronic POPs, their photofunctions are quite limited as a result of aggregation‐caused excitation energy dissipation. To solve this problem, a general strategy for designing highly emissive photofunctional POP films has been explored . The strategy for the structural design is to integrate three functional segments, including TPE core ( 38 ), twisted linkers and electropolymerizable N ‐substituted carbazole peripheral units into well‐defined porous π‐networks (Figure b, 39 ).…”

Electrochemically Generated Thin Films of Microporous Polymer Networks: Synthesis, Properties, and Applications

“…a) Fluorescence quantum yields of monomer 10 in THF solution or as spin‐coated film, and of electrogenerated microporous P10 films of different thicknesses, b) degree of PL quenching of P10 films upon after interaction with various electron‐poor nitroarenes in acetonitrile, c) spectral PL changes of a P10 film (thickness of 5 nm) upon immersion in TNP solutions in acetonitrile (1 min), and d) reversibility of the TNP sensing approach ( P10 films, thickness 10 nm). Adapted with permission …”