Red-Shift (2-Hydroxyphenyl)-Benzothiazole Emission by Mimicking the Excited-State Intramolecular Proton Transfer Effect

Novel strategies to optimize the photophysical properties of organic fluorophores are of great significance to the design of imaging probes to interrogate biology. While the 2-(2-hydroxyphenyl)-benzothiazole (HBT) fluorophore has attracted considerable attention in the field of fluorescence imaging, its short emission in the blue region and low quantum yield restrict its wide application. Herein, by mimicking the excited-state intramolecular proton transfer (ESIPT) effect, we designed a series of 2-(2-hydroxyphenyl)-benzothiazole (HBT) derivatives by complexing the heteroatoms therein with a boron atom to enhance the chance of the tautomerized keto-like resonance form. This strategy significantly red-shifted the emission wavelengths of HBT, greatly enhanced its quantum yields, and caused little effect on molecular size. Typically, compounds 12B and 13B were observed to emit in the near-infrared region, making them among the smallest organic structures with emission above 650 nm.

Organic Fluorophores for 1064 nm Excited NIR-II Fluorescence Imaging

Second near-infrared window (NIR-II) fluorescence imaging has shown great potential in the field of bioimaging. However, the excitation wavelengths of most NIR-II fluorescence dyes are in the first near-infrared (NIR-I) region, which leads to limited imaging depth and resolution. To address such issue, NIR-II fluorescence dyes with 1,064 nm excitation have been developed and applied for in vivo imaging. Compared with NIR-I wavelength excited dyes, 1,064 nm excited dyes exhibit a higher tissue penetration depth and resolution. The improved performance makes these dyes have much broader imaging applications. In this mini review, we summarize recent advances in 1,064 nm excited NIR-II fluorescence fluorophores for bioimaging. Two kinds of organic fluorophores, small molecule dye and semiconducting polymer (SP), are reviewed. The general properties of these fluorophores are first introduced. Small molecule dyes with different chemical structures for variety of bioimaging applications are then discussed, followed by the introduction of SPs for NIR-II phototheranostics. Finally, the conclusion and future perspective of this field is given.

Boranils: Versatile Multifunctional Organic Fluorophores for Innovative Applications

Multifunctional stimuli-responsive fluorophores showing bright environment-sensitive emissions have fueled intense research due to their innovative applications in the fields of biotechnologies, optoelectronics, and materials. A strong structural diversity is observed among molecular materials, which has been enriched over the years with a growing responsiveness to stimuli. Boron dipyrromethene (BODIPY) dyes have long been the flagship of emissive boron complexes due to their outstanding properties until a decade ago when analogues based on N^O, N^N, or N^C π-conjugated chelates emerged. The finality of developing borate dyes was to compensate for BODIPYs’ lack of solid-state fluorescence and small Stokes shifts while keeping their excellent optical properties in solution. Among them, the borate complexes based on a salicylaldimine ligand, called by the acronym boranils appear as the most promising, owing to their facile synthesis and dual-state emission properties. Boranil dyes have proven to be good alternatives to BODIPY dyes and have been applied in applications such as bioimaging, bioconjugation, and detection of biosubstrates. Meanwhile, ab initio calculations have rationalized experimental results and provided insightful feedback for future designs. This review article aims at providing a concise yet representative overview of the chemistry around the boranil core with the subsequent applications.

Designing Highly Luminescent Molecular Aggregates via Bottom-Up Nanoscale Engineering

Coupling of excitations between organic fluorophores in J-aggregates leads to coherent delocalization of excitons across multiple molecules, resulting in materials with high extinction coefficients, long-range exciton transport, and, in particular, short radiative lifetimes. Despite these favorable optical properties, uses of J-aggregates as high-speed light sources have been hindered by their low photoluminescence quantum yields. Here, we take a bottom-up approach to design a novel J-aggregate system with a large extinction coefficient, a high quantum yield and a short lifetime. To achieve this goal, we first select a J-aggregating cyanine chromophore and reduce its nonradiative pathways by rigidifying the backbone of the cyanine dye. The resulting conformationally-restrained cyanine dye exhibits strong absorbance at 530 nm and fluorescence at 550 nm with 90% quantum yield and 2.3 ns lifetime. We develop optimal conditions for the self-assembly of highly emissive J-aggregates. Cryogenic transmission electron microscopy (cryo-TEM) and dynamic light scattering (DLS) reveal micron-scale extended structures with 2D sheet-like morphology, indicating long-range structural order. These novel J-aggregates have a strong red-shifted absorption at 600 nm, resonant fluorescence with no Stokes shift, 50% quantum yield, and 220 ps lifetime at room temperature. We further stabilize these aggregates in a glassy sugar matrix and study their excitonic behavior using temperature-dependent absorption and fluorescence spectroscopy. These temperature- dependent studies confirm J-type excitonic coupling and superradiance. Our results have implications for the development of a new generation of organic fluorophores that combine high speed, high quantum yield and solution processing.