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Cancer metastasis remains a critical factor contributing to the current limitations in cancer treatment. Photothermal immunotherapy has emerged as a safe and potent therapeutic approach, demonstrating the capability to suppress tumor growth and metastasis. While researchers have extensively investigated various structural modifications to enhance photothermal conversion performance, the influence of molecular configuration has received comparatively limited attention. In this study, we synthesized two isomers, CZTBT and LVTBT, which possessed distinct configurations. LVTBT, characterized by a flatter molecular configuration, exhibited an extended absorption wavelength and a higher molar extinction coefficient. Its excited state facilitated stronger rotation for non‐radiative transitions, leading to a high photothermal conversion efficiency (PCE) of 36.3 %. When combined with R848, LVTBT@R848 nanoparticles (NPs)‐mediated photothermal immunotherapy functioned as an in situ tumor vaccine, promoting the maturation of dendritic cells (DCs), T cell infiltration, and the differentiation of natural killer (NK) cells and memory T cells, thereby activating the strong immune response. Consequently, it significantly inhibited the growth of both primary and distant tumors, while also limiting lung metastasis. In summary, this study proposed a configuration‐mediated non‐radiative transition strategy for efficient photothermal immunotherapy, advancing the frontiers of organic photothermal agents (OPTAs) design and synthesis. [ABSTRACT FROM AUTHOR]

Fluorescence lifetime imaging has been a powerful tool for biomedical research. Recently, fluorescence lifetime‐based multiplexing imaging has expanded imaging channels by using probes that harbor the same spectral channels and distinct excited state lifetime. While it is desirable to control the excited state lifetime of any given fluorescent probes, the rational control of fluorescence lifetimes remains a challenge. Herein, we chose boron dipyrromethene (BODIPY) as a model system and provided chemical strategies to regulate the fluorescence lifetime of its derivatives with varying spectral features. We find electronegativity of structural substituents at the 8′ and 5′ positions is important to control the lifetime for the green‐emitting and red‐emitting BODIPY scaffolds. Mechanistically, such influences are exerted via the photo‐induced electron transfer and the intramolecular charge transfer processes for the 8′ and 5′ positions of BODIPY, respectively. Based on these principles, we have generated a group of BODIPY probes that enable imaging experiments to separate multiple targets using fluorescence lifetime as a signal. In addition to BODIPY, we envision modulation of electronegativity of chemical substituents could serve as a feasible strategy to achieve rational control of fluorescence lifetime for a variety of small molecule fluorophores. [ABSTRACT FROM AUTHOR]

Herein, a novel molecular SO2‐Bri‐DSB based on the sulfone‐bridged distyrylbenzene derivative is synthesized, and its organic crystal is fabricated. It has a very high photoluminescence (PL) quantum efficiency in the solution and crystalline state, i.e., dual‐state emission (DSE), and the corresponding PL mechanism is clarified in detail using the transient absorption and transient PL test. The PL behaviors in the monomolecular state and organic crystal are compared. In addition, the optical anisotropy of the SO2‐Bri‐DSB crystal is thoroughly investigated using various polarization‐dependent spectroscopy techniques. The time evolution of anisotropy is composed of a step behavior caused by the anisotropy of the electronic transition and a slow enhancing process with a lifetime of 4.86 ns, which is governed by the change in emission lifetime due to the anisotropy. The space‐resolved evolution of the optical anisotropy is investigated using the polarization‐dependent light wave‐guiding test and exhibits that the emission anisotropy gradually decreases with length, and it has a longer effective propagation length than the polarization emission signal. The findings provide insight into the intrinsic optical anisotropy of single‐molecular crystals and indicate that these materials have enormous potential in the domains of polarization lighting and display. [ABSTRACT FROM AUTHOR]