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Fluorophores emitting in the second near-infrared window (NIR-II, 900–1700nm) allow for high-resolution deep-tissue bioimaging owing to minimal tissue scattering. Although J-aggregation offers a promising approach to developing long-wavelength emitters, the scarcity of J-type backbones and reliable design principles limits their application in biological imaging. Here, we introduce a strategy for engineering high-brightness NIR-II J-aggregated fluorophores by incorporating electron-withdrawing substituents into a fused-ring backbone. These substituents modulate the electrostatic potential (ESP) distribution across the conjugated backbone, reducing both electrostatic repulsion and intermolecular distance, which promotes ordered J-aggregation. As a result, Y8 aggregate (Y8 nanoparticles) exhibits an outstanding fluorescence quantum yield of up to 12.9% and strong near-infrared absorption in aqueous solution for high-performance NIR-II fluorescence imaging in vivo. This work not only presents a novel J-type backbone but also advances the understanding of the structure–property relationship critical to designing NIR-II J-aggregates.

The sol-gel method has been employed in the fabrication of mesoporous composite films consisting of a nonionic surfactant, Pluronic P123, as the organic component, and silica as the inorganic component. The hybrid nature of these films resulted in their having an internal structure consisting of nanometer size self-assembled organic mesostructures surrounded by a silica framework. These films served as the host matrix for the laser dye coumarin 481 (C481) and an energy transfer complex formed between C481 and J-aggregated meso-tetra(4-sulfonatophenyl)porphyrin (TSPP). Upon exposure to methanol vapor, a rapid and reversible decrease in fluorescence intensity occurs for films containing C481 alone as well as containing both C481 and TSPP. Steady-state and time-resolved spectroscopic studies suggest that the decrease in fluorescence intensity is primarily due to an excited state interaction between methanol and C481; while, additionally, morphological changes within the film appear to play a role for films containing both C481 and TSPP.

The interactions of two amphiphilic porphyrins with anionic surfactant sodium bis(2-ethylhexyl)sulfosuccinate (AOT) in aqueous solutions were studied by UV-vis absorption spectroscopy, fluorescence spectroscopy, resonance light scattering technique, fluorescence anisotropy and surface tension measurements. The two porphyrins, meso-tetra(4-hydroxyphenyl)porphyrin (THPP) and meso-tetra(3,5-dibromo-4-hydroxylphenyl)porphyrin (T(DBHP)P), exist as irregular aggregates in aqueous solutions with a broad and low absorption peak near the maximum of monomer peak. The interaction of THPP with AOT leads to the formation of a fluorescent aggregate of porphyrin which was assigned as J-type aggregate according to exciton theory. A long red-shifted Soret band together with a new strong Q-band, a broad emission peak and a sharply peaked resonance light scattering signal are observed for this J-aggregate. The formation of J-aggregate is independent of the initial THPP concentration and can be influenced greatly by ionic strength. The aggregation kinetics has been investigated by UV-vis absorption spectroscopy and fluorescence anisotropy. Conversion of the porphyrin monomers to J-aggregate is observed. The addition of THPP increases the surface tension of solution and changes the critical micelle concentration of AOT. J-aggregate was not observed for T(DBHP)P in AOT solutions which only shows solubilization. The mechanism of aggregation was discussed.

Self-aggregation processes are rarely reproducible owing to their dependence on various experimental parameters (aging of stock solutions, their concentration, concentration of working solutions, ionic strength, etc.). However, by enucleating the dependence from one parameter (in this case, the dependence of aggregation from the concentration of the working solutions), it has been possible to hierarchically control self-aggregation of the protonated form of tetrakis-(4-sulfonatophenyl)-porphyrin.

The effect of water on the spectroscopic behaviors of meso-tetrakis-(4-sulfonatophenyl) porphyrin (TPPS) in acidic 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF₄) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄) is investigated by spectroscopic methods. In acidic ionic liquids without water, the Soret bands of the protonated form (H₄TPPS^2-) and J-aggregates of TPPS are centered at 449 and 469 nm, respectively, and the Q-band is centered at 679 nm. When increasing the content of water, the Soret band of H₄TPPS^2- is blue-shifted to 430 nm. However, the Soret and Q-bands of J-aggregates are red-shifted to 487 and 701 nm, respectively. The NMR and pyrene-scale polarity experiments reveal that the change of the bulk environment is responsible for the red-shift of J-aggregates and the blue-shift of H₄TPPS^2-. According to the analysis of the fluorescence spectra, the content of H₄TPPS^2- increases gradually with the addition of water, while the content of H₂TPPS^4- takes the opposite trend. Simultaneously, the content of J-aggregates decreases substantially when the addition of water is 0 ~ ca. 12 μL (or 13 μL) but it decreases slowly with further addition of water. Remarkably, the fluorescence intensity of J-aggregates is relatively strong. In addition, the fluorescence of J-aggregates can be detected when λ_ex is set at both λ_ex for TPPS monomers and λ_ex for J-aggregates. While the fluorescence of TPPS monomers can be detected only when λ_ex is set at λ_ex for monomers. Moreover, with the addition of water, the fluorescence lifetimes of H₂TPPS^4- and H₄TPPS^2- increase from 3.202 and 0.830 ns to 9.623 and 2.964 ns, respectively.

A water-soluble porphyrin bearing multi-dentate ligands was prepared, and its aggregation behavior in solution under various conditions (temperature, pH, metal ion, chiral compound) was investigated using UV-vis absorption spectroscopy, fluorescence spectroscopy, circular dichroism (CD) spectroscopy. Upon the addition of Ca²⁺, Ba²⁺, or Sr²⁺ to a solution of porphyrin, the porphyrin first forms an H-aggregate and is then transformed to a J-aggregate at 25 °C in buffered aqueous solution (pH 7.4). On the other hand, the porphyrin forms a self-aggregate (H-aggregate) at 25 °C in buffered aqueous solution (pH 6.0), and the H-aggregate does not form the J-aggregate upon the addition of the group II metal ions. The measurement of CD spectra revealed that the H-aggregate that forms right after the addition of Ba²⁺ to the porphyrin solution in the presence of D- or L-phenylalanine does not show an induced CD signal, while the J-aggregate formed from the H-aggregate shows induced CD signals in the Soret region.

The crystal structures of three analogs of trans-DPDSB (2,5-diphenyl-1,4-distyrylbenzene with two trans double bonds) are very similar to that of rubrene, which have face-to-face molecular packing mode with relative displacement along the molecular long axis. The very strong intermolecular π-π interactions enable the crystal to have the potential of high charge-carrier mobility predicted by the theoretical calculations. Most important, the crystals of these materials have very high photoluminescence (PL) efficiency of about 50% due to the J-type dipole stacking, which is different from the crystal of rubrene. The crystal structures give the prediction of combining both high luminescence and high mobility in one crystal by constructing J-type dipole stacking with strong π-π interactions.

The sol-gel method has been employed in the fabrication of mesoporous composite films consisting of a nonionic surfactant, Pluronic P123, as the organic component, and silica as the inorganic component. The hybrid nature of these films resulted in their having an internal structure consisting of nanometer size self-assembled organic mesostructures surrounded by a silica framework. These films served as the host matrix for the laser dye coumarin 481 (C481) and an energy transfer complex formed between C481 and J-aggregated meso-tetra(4-sulfonatophenyl)porphyrin (TSPP). Upon exposure to methanol vapor, a rapid and reversible decrease in fluorescence intensity occurs for films containing C481 alone as well as containing both C481 and TSPP. Steady-state and time-resolved spectroscopic studies suggest that the decrease in fluorescence intensity is primarily due to an excited state interaction between methanol and C481; while, additionally, morphological changes within the film appear to play a role for films containing both C481 and TSPP.