Restricted Aggregate Formation on Tetraphenylethene-Substituted Polythiophenes

Abstract

Two new polythiophenes functionalized with different degrees of tetraphenylethene, TPE, side groups (with TPE moieties at each thiophene unit, homoPT, and one in which only each second thiophene unit carries a TPE side chain, coPT) were successfully synthesized and characterized together with a poly(3hexylthiophene) with similar average molecular weight and a tetraphenylethene-thiophene model compound. The study aimed to understand the role of the sterically bulky TPE pendant groups on the inhibition of intra-and/or interchain packing (aggregation) of these conjugated polymers. For the tetraphenylethenethiophene model, compound aggregation induced emission (AIE) is active for water fractions ≥ 90%. An opposite behavior is found for the polythiophenes (homoPT and coPT) where aggregation caused quenching (ACQ) was found to occur both in solution and in the solid state. For the polythiophene with the higher degree of TPE labeling, homoPT, the amount of ACQ is significantly decreased. This is attributed to the high TPE substitution density in the polymer which promotes a more twisted conformation of the polymer backbone as the emissive chromophore. For the TPE-polythiophenes, only the energy migration mechanism was found to be active since the bulky TPE substituents restrict the polymer's intramolecular motions. The experimental observations of a small shift in the emission spectra of homoPT and significant hindering of ACQ on going from solution to the solid state explain the absence of intermolecular interactions together with the restriction of intramolecular rotations.

Realizing highly efficient blue photoluminescence of dimethylsilane-aryl (phenylene, diphenylene, fluorenyl) main-chain polymers with σ–π conjugation

“…Considerable efforts have been devoted to overcome the existing barriers to a certain extent. 35,36 However, achieving high quantum efficiency, easy film-forming ability and high charge carrier mobility in organosilicon polymers still remains challenging.…”

Pressure Dependence on the Thermal Conductivity of H‐ and J‐type Nanocomposites

“…[ 27,28 ] Therefore, as the external pressure increases, the maximal fluorescence emission wavelength (λ max ) blueshifts when the TPE derivatives form H‐type aggregates, whereas it redshifts when the TPE derivatives form J‐type aggregates. [ 22,29–33 ]…”

“…[27,28] Therefore, as the external pressure increases, the maximal fluorescence emission wavelength (λ max ) blueshifts when the TPE derivatives form H-type aggregates, whereas it redshifts when the TPE derivatives form J-type aggregates. [22,[29][30][31][32][33] The available methods for achieving high heat dissipation by encapsulating electronic components in epoxy molding compounds (EMCs) are improving steadily, which enables packaging semiconductors to prevent damage and efficiently remove internally generated heat. [34,35] EMC components are molded via transfer or injection molding processes, wherein the epoxy (EP) is exposed to high temperatures and pressures.…”

Tuning the Behavior of a Hydrotalcite-Supported Sulfonated Bithiophene from Aggregation-Caused Quenching to Efficient Monomer Luminescence

“…[11][12][13][14][15][16] However, when aggregation is not well-controlled, significant aggregation-caused quenching (ACQ) appears due to the formation of less emissive species. 17 Challenging issues are therefore to control the domain separation at a supramolecular level and the randomness in orientation of the fluorophores. 18 This approach takes its inspiration from crucial life processes where clusters or aggregates of individual elements are held together by weak intermolecular forces and are considered as single units.…”

“…However, when aggregation is not well-controlled, significant aggregation-caused quenching (ACQ) appears due to the formation of less emissive species . Challenging issues are therefore to control the domain separation at a supramolecular level and the randomness in orientation of the fluorophores .…”