Near‐infrared‐emitting polymers were prepared using four boron‐difluoride‐curcuminoid‐based monomers using ring‐opening metathesis polymerization (ROMP). Well‐defined polymers with molecular weights of ≈20 kDa and dispersities <1.07 were produced and exhibited near‐infrared (NIR) emission in solution and in the solid state with photoluminescence quantum yields (ΦPL) as high as 0.72 and 0.18, respectively. Time‐resolved emission spectroscopy revealed thermally activated delayed fluorescence (TADF) in polymers containing highly planar dopants, whereas room‐temperature phosphorescence dominated with twisted species. Density functional theory demonstrated that rotation about the donor–acceptor linker can give rise to TADF, even where none would be expected based on calculations using ground‐state geometries. Incorporation of TADF‐active materials into water‐soluble polymer dots (Pdots) gave NIR‐emissive nanoparticles, and conjugation of these Pdots with antibodies enabled immunofluorescent labeling of SK‐BR3 human breast‐cancer cells.
A series of acrylic donor and acceptor monomers were prepared to investigate the effect of electronic and structural changes on the through-space charge-transfer (TSCT) thermally activated delayed fluorescence (TADF) phenomenon. Donor (D) and acceptor (A) monomers were copolymerized using a Cu(0) reversible-deactivation radical polymerization (RDRP) approach, resulting in nonconjugated polymers with molecular weights between 8 and 21 kDa and dispersities below 1.3. Many of the resulting polymers were found to exhibit TSCT TADF, while in several cases, phosphorescence appeared to dominate. Aggregation-induced emission was also observed in many cases, consistent with a TSCT mechanism requiring close D−A contact. The results indicate that the propensity for TSCT TADF of a given D−A pair cannot be predicted solely based on the value of the singlet−triplet energy gap (ΔE ST ) or the frontier orbitals of the monomers and that steric considerations are likely critical for efficient TSCT.
Near‐infrared‐emitting polymers were prepared using four boron‐difluoride‐curcuminoid‐based monomers using ring‐opening metathesis polymerization (ROMP). Well‐defined polymers with molecular weights of ≈20 kDa and dispersities <1.07 were produced and exhibited near‐infrared (NIR) emission in solution and in the solid state with photoluminescence quantum yields (ΦPL) as high as 0.72 and 0.18, respectively. Time‐resolved emission spectroscopy revealed thermally activated delayed fluorescence (TADF) in polymers containing highly planar dopants, whereas room‐temperature phosphorescence dominated with twisted species. Density functional theory demonstrated that rotation about the donor–acceptor linker can give rise to TADF, even where none would be expected based on calculations using ground‐state geometries. Incorporation of TADF‐active materials into water‐soluble polymer dots (Pdots) gave NIR‐emissive nanoparticles, and conjugation of these Pdots with antibodies enabled immunofluorescent labeling of SK‐BR3 human breast‐cancer cells.
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