A BODIPY‐Based Donor/Donor–Acceptor System: Towards Highly Efficient Long‐Wavelength‐Excitable Near‐IR Polymer Dots with Narrow and Strong Absorption Features

: Bright long-wavelength-excitable semiconducting polymer dots (LWE-Pdots) are highly desirable for in vivo imaging and multiplexed in vitro bioassays. LWE-Pdots have been obtained by incorporating a near-infrared (NIR) emitter into the backbone of a polymer host to develop a binary donor-acceptor (D-A) system. However, they usually suffer from severe concentration quenching and a trade-off between fluorescence quantum yield (Φf ) and absorption cross-section (σ). Herein, we describe a ternary component (D1 /D2 -A) strategy to achieve ultrabright, green laser-excitable Pdots with narrow-band NIR emission by introducing a BODIPY-based assistant polymer donor as D1 . The D1 /D2 -A Pdots possess improved Φf and σ compared to corresponding binary D2 -A Pdots. Their Φf is as high as 40.2 %, one of the most efficient NIR Pdots reported. The D1 /D2 -A Pdots show ultrahigh single-particle brightness, 83-fold brighter than Qdot 705 when excited by a 532 nm laser. When injected into mice, higher contrast in vivo tumor imaging was achieved using the ternary Pdots versus the binary D-A Pdots.