High molar absorption coefficients (ε) in the near-infrared (NIR) region are critical for maximizing light-harvesting efficiency, enabling deep-tissue penetration, and enhancing reactive oxygen species (ROS) generation in phototheranostics. However, strong absorptivity at NIR wavelengths is challenging for organic luminogens due to intrinsically diminished oscillator strengths. We report a symmetry-guided molecular engineering approach to construct octupolar aggregation-induced emission luminogens (AIEgens) that overcome this limitation. Incorporating fused tetrahydroxanthylium (THX) acceptors into a D(A)₃ framework yields a four-fold enhancement in ε (5.47 × 10⁴ M⁻¹ cm⁻¹) at 670 nm compared to dipolar analogs (D-A), while achieving bright NIR-II emission at 963 nm. Femtosecond transient absorption spectroscopy reveals stronger ground-state bleaching and additional excited-state absorption in octupolar systems, correlating with enhanced light-harvesting. Density functional theory calculations demonstrate that symmetry-enabled dipole coupling activates additional S₀→S₂ transitions, explaining the high absorptivity. The octupolar architecture also reduces ΔE_ST and introduces low-lying excited states, promoting intersystem crossing and boosting ROS generation. This symmetry-driven design combines twisted conformations with AIE features to create a robust platform for bright NIR-II emission and advanced phototheranostic applications.

Suppressing nonradiative decay is crucial for achieving high photoluminescence quantum yields (PLQYs) in light-emitting materials. Although high-performance optical materials have been explored in the past decades, the specific dissipation pathways of their nonradiative channels remain unclear. This work unveils the energy dissipation mechanisms of excited states at the microscopic molecular level, achieving singlet-state vibration decoupling through intramolecular through-space charge transfer (TSCT), thereby promoting efficient fluorescence emission. Moreover, the rigid environment and multiple noncovalent interactions (e.g., hydrogen bonding and electrostatic complementarity) provided by the polymer matrix effectively restrain the vibrational motion of the chromophores, creating favorable conditions for triplet-state room-temperature phosphorescence (RTP). Experimental and theoretical results demonstrate that TSCT-induced vibration decoupling is key to the high-efficiency fluorescence of 1 Np, while the planar rigid structure of TPNp dispersed in the polymer enables long-lived blue RTP with a lifetime of τ_P = 1.96 s. This study systematically elucidates the multipathway energy dissipation mechanisms in photon radiative decay and provides a refined theoretical framework for a deeper understanding of excited-state dynamics in photo-functional materials.

Aggregate science, which studies how molecular aggregates exhibit properties distinct from those of individual molecules, is fundamental to understanding molecular interactions in various fields, including chemistry, physics, and the life sciences. However, precisely controlling aggregate structures and their properties without altering intrinsic molecular properties remains a significant challenge. Here, we report a versatile platform built on a unique mesoionic luminogen, TPO (thiazolo[3,2-a]pyridin-4-ium-3-olate), to systematically investigate and modulate structure-property relationships in aggregates. By introducing alkyl chains of varying lengths, three TPO derivatives (TPO-X, X = 2, 8, or 12) enable fine-tuning of aggregate morphologies and photophysical behaviors. Mechanistic studies reveal that intermolecular interactions between the TPO core govern excited-state energy pathways, leading to distinct emission properties and reactive oxygen species (ROS) generation abilities. Moreover, TPO-X showed distinct organelle targeting abilities: TPO-2 for mitochondria, TPO-8 for endoplasmic reticulum, and TPO-12 for the cell membrane, respectively. Furthermore, TPO-X achieved excellent tumor cell killing effects via different cell death pathways. This mesoionic core demonstrates robust abilities for the regulation of novel aggregate materials in various research fields.

Carbon dots (CDs) have garnered widespread interest in biosensing, optoelectronics, and biomedicine due to their exceptional fluorescence, biocompatibility, and low cost. While individual CDs exhibit tunable properties, their organization into higher-order architectures via self-assembly enables emergent collective functionalities that are inaccessible to discrete nanoparticles. This review presents a systematic overview of the design principles and recent advances in CD self-assembly. We first summarize synthetic strategies and the morphological evolution of assemblies, spanning zero-dimensional nanoparticles to three-dimensional macroscopic materials. We then discuss how self-assembly modulates photophysical properties, followed by an analysis of the underlying supramolecular mechanisms. Subsequently, representative applications enabled by these assemblies are highlighted. Finally, we outline key challenges related to scalability, stability, and the prediction of structure-property relationships, and provide an outlook on leveraging self-assembly to fully realize the potential of CDs for advanced functional materials.

Self-trapped excitons (STEs) are generating significant interest due to their broadband emission and self-absorption-free advantages. However, achieving high-efficiency singlet/triplet STE near-infrared (NIR) emissive tuning remains challenging issues that originate from energy gap law and large Stokes shift. Herein, novel manganese iodide dimers have been demonstrated in CsI crystalline matrix with high photoluminescence quantum yields of 18% and 25% for singlet and triplet STE emissions up to 1200 nm, respectively, where ultrafast spin-flip process from triplet to singlet excited states is realized via Pb²⁺-doping strategy. Temperature-dependent steady-state, electron paramagnetic resonance, femtosecond transient absorption spectroscopic techniques and theoretical calculations verify intersystem crossing, and reverse intersystem crossing (RISC) processes are governed by the interplay between spin-orbit coupling (SOC) and Jahn-Teller (JT) effect. RISC is accelerated by enhanced SOC due to heavy-atom effects (Pb and I), suppressed JT distortions, and reduced excited-state structural reorganization, leading to RISC rate as fast as 6.7 × 10¹¹ s^‒1, more than two-order-of-magnitude enhancement before Pb doping. Moreover, a unified framework is developed including Mn²⁺-Mn²⁺ ion pair, molecular orbital, and configurational coordinate diagram to interpret STE-based NIR emissions in 0D systems. These findings gain deep insights into ultrafast STE dynamics for designing highly emissive NIR materials toward photonic applications.

In situ vaccination is a promising strategy for personalized cancer immunotherapy; however, its efficacy is often limited by rapid antigen degradation, inefficient delivery to lymph nodes (LNs), and the immunosuppressive tumor microenvironment (TME). To overcome these challenges, we developed a versatile in situ cancer nanovaccine by conjugating the TLR7/8 agonist R848 to a polymeric immunogenic cell death (ICD) inducer, termed G4P-C7A-R848. In aqueous solution, G4P-C7A-R848 self-assembles into nanoparticles (PCR-NPs), which accumulate at tumor sites following systemic administration. Within tumors, PCR-NPs trigger the release of tumor-associated antigens from tumor cells via ICD and subsequently capture them to form an in situ nanovaccine. These nanovaccines then traffic to tumor-draining LNs (TDLNs), where they promote dendritic cell maturation and T cell activation. Moreover, the nanovaccine reprograms macrophages toward the tumoricidal M1 phenotype, thereby alleviating immunosuppression in the TME. This coordinated action enhances the infiltration and activation of CD8⁺ T cells, leading to robust and durable antitumor immunity. Across multiple murine tumor models, PCR-NPs treatment resulted in significant tumor regression and prolonged survival. This study offers a simple yet effective platform for developing potent in situ cancer vaccines.

Carbon dots (CDs) have garnered significant attention for their excellent and versatile optical properties. Nevertheless, the influence of aggregation states on the photophysical properties of CDs has not yet been systematically elucidated. Herein, we present a systematic investigation into the aggregation-dependent photophysical behavior of CDs with a Si-O-Si-encapsulated luminescent carbon core and surface long-chain fatty amines. This study reveals two distinct pathways for emission modulation: (1) achieving concentration-dependent photoluminescence for CDs, spanning from green (λ_em = 527 nm) to deep red (λ_em = 672 nm); and (2) inducing the self-assembly of CDs into size-tunable nano- to micro-scale spherical structures in a poor solvent, which exhibit aggregation-induced emission with a maximum photoluminescence quantum yield of 87.6%. This unique dual-mode aggregation-dependent photoluminescence enables the successful application of CDs in rewritable water‑jet printing, highlighting their strong potential for practical uses.

Luminescent liquid crystals (LCs), combining liquid crystalline order and luminescent properties, provide new opportunities for advanced materials. However, the traditional strategy to obtain luminescent LCs is often accompanied by aggregation-caused quenching, tedious synthesis, environmental hazards, and so on. In this work, we have studied the construction of LCs with clusterization-triggered emission (CTE) that can address the above issues and further can manipulate LC behavior and clusteroluminescence by host−guest interactions. The liquid crystal mesogen B-Chol formed a thermotropic LC with CTE character. The birefringence was changed and the chirality was inverted when B-Chol was protonated to B-Chol-H. Interestingly, after complexation with 1,4-dimethoxypillar[5]arene (DMP5), it changed into a crystalline phase with chirality inversion and CTE enhancement. Importantly, the quenching of clusteroluminescence, the inversion of chirality, and change of birefringence were achieved by adding acid due to the host−guest complexation between DMP5 and B-Chol-H. Furthermore, this regulatable clusteroluminescent LC system was successfully applied in the field of information encryption. This combination of clusteroluminescence, liquid crystals, and stimuli-responsiveness demonstrates the potential of nonconventional luminescent LCs as a promising platform for advanced anticounterfeiting and secure communication.

Phototheranostics represent a pivotal modality for the concurrent diagnosis and treatment of malignant tumors. The development of high-performance phototheranostic agents has therefore become increasingly imperative. In this work, a “unity of a thousand blades” phototheranostic nanoplatform (TDTIC-M) with aggregation-induced emission (AIE) properties was synthesized through an extended electronic π-bridge strategy to enhance the Stokes shift and multimodal image-guided combined Type I/II photodynamic therapy and photothermal therapy (Type I/II PDT-PTT) synergistic phototherapy for breast cancer. Specifically, the target compounds (TIC-M, TTIC-M, and TDTIC-M) with donor-acceptor distorted conformations were prepared by a Knoevenagel coupling reaction. The TDTIC-M derivative, which incorporates two thiophene units as the π-bridge, boasts enhanced optical characteristics relative to both TIC-M and TTIC-M. This derivative was further encapsulated within DSPE-PEG₂₀₀₀ to form TDTIC-M nanoparticles (NPs) with good biocompatibility. Such NPs exhibit a large Stokes shift (∼270 nm), robust reactive oxygen species generation (¹O₂, ·OH, and ·O₂⁻), and a notable photothermal conversion efficiency (27.93%). Furthermore, TDTIC-M NPs demonstrate precise lysosome-targeted capacity and excellent phototherapy effects in vitro and effectively regulate the expression of apoptosis-related proteins (Caspase3, Bax, and Bcl-2). Moreover, TDTIC-M NPs demonstrate an exceptional multimodal imaging effect and synergistic phototherapy effect through integrating Type I/II PDT with PTT. Consequently, TDTIC-M emerges as a highly prospective phototheranostic candidate for multimodal imaging-guided cancer phototherapy.

Molecular aggregation profoundly alters the optical properties of fluorophores, yet its behavior in dynamic biological environments remains insufficiently understood and rarely harnessed functionally. Here, we report a membrane-controlled aggregation strategy based on plasma membrane-targeted BODIPY dimers engineered to undergo tunable H - and J-aggregation. By modulating the linker length, we establish a clear structure-aggregation relationship in which dimers form intramolecular H-aggregates in polar media, while two-dimensional confinement within lipid bilayers promotes intermolecular aggregation with red-shifted emission. Quantitative studies in model membranes reveal a threshold-dependent transition toward aggregate formation above a probe/lipid ratio of 1/100, highlighting the lipid bilayer as an active supramolecular platform that enhances probe-probe encounters and favors emissive excitonic states. In live cells, this membrane-promoted J-aggregation generates spontaneous blinking behavior that enables dual-channel single-molecule localization microscopy without specialized imaging buffers. Mechanistic investigations using HaloTag constructs confirm that while intramolecular aggregation can occur, membrane-driven intermolecular collisions strongly amplify J-aggregate formation. These findings demonstrate that biological membranes can serve as dynamic two-dimensional reactors for excitonic coupling, and establish membrane-induced J-aggregation of small-molecule fluorophores as a functional and generalizable principle for bioimaging.

While through-space conjugation (TSC) offers a powerful paradigm for constructing luminescent materials beyond planar π-systems, its deliberate integration and activation within conventional chromophoric frameworks to enhance emission remains a fundamental challenge. We address this by designing siloxane-linked fluorescent polymers (SFPs), synthesized via straightforward Heck reactions using 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and bi-, tri-, or tetra-brominated aromatic monomers. The siloxane linkage is not merely a passive spacer but actively mediates efficient TSC, endowing the polymers with remarkable dual-state emission. Notably, spirobifluorene-based polymer SFP-2 achieves photoluminescence quantum yields of up to 92.7% in solution and 23.4% in the solid state. Theoretical and spectroscopic analyses elucidate a “dynamic encapsulation” mechanism, wherein the flexible siloxane chain wraps two chromophores into a spatially proximate, non-covalently coupled assembly. This configuration suppresses intramolecular vibrational relaxation in solution, while chain entanglement in the solid state creates isolated microenvironments that inhibit aggregation-caused quenching. Leveraging this unique photophysics, the materials function as selective “turn-off” fluorescence probes for trifluralin detection under daylight and UV light, and as effective components in UV-shielding films. This work establishes a general “siloxane-activated TSC” design strategy, fundamentally underscores the active role of siloxanes in modulating optoelectronic properties, and highlights their potential in flexible electronics and sensing technologies.

Photodynamic therapy (PDT) is a promising cancer treatment with minimal invasiveness and high selectivity, but its efficacy depends heavily on subcellular reactive oxygen species (ROS) localization. Although organelle-targeted PDT can enhance antitumor effects, systematic evaluation and comparison of their photocytotoxicity, and photoimmunological activation capacity remain lacking. Herein, we synthesized four organelle-targeted photosensitizers (PSs) using pyropheophorbide a (Ppa) as the core scaffold: Ppa-Mit, Ppa-Lys, Ppa-ER, and Ppa-Nuc, which target mitochondria, lysosomes, endoplasmic reticulum (ER), and nucleus, respectively. These PSs were then individually encapsulated into synthetic high-density lipoprotein (sHDL) nanodiscs to yield PMN, PLN, PEN, and PNN. All nanodiscs achieved specific organelle targeting. Photocytotoxicity followed the order PLN > PMN > PNN > PEN, while PMN exhibited the optimal immunogenic cell death (ICD)-inducing capacity by triggering robust secretion of damage-associated molecular patterns (DAMPs). In vivo, PMN and PLN achieved complete, recurrence-free tumor ablation, promoting infiltration of mature dendritic cells, and cytotoxic CD8⁺ T cells (expressing Granzyme B) to elicit strong antitumor immunity. This study identifies PMN and PLN as promising PDT agents and highlights mitochondria-targeted and lysosome-targeted PDT as a favorable approach for effective tumor photoimmunotherapy, providing guidance for the rational design of targeted PSs.

Thiolate-protected gold nanoclusters occupy a unique domain between molecular complexes and metallic nanoparticles, exhibiting size-specific electronic structure, ligand-mediated stability, and emergent collective behavior during synthesis. This work introduces and validates a machine learning-driven strategy to predict atomistic coalescence mechanisms of self-assembly of gold-thiolate nanoclusters across a significant size range of products (A₃₆-Au₈₅₁) and thermal conditions (500-700 K). We used an atomic cluster expansion interatomic potential trained on density functional theory data, enabling molecular dynamics simulations up to 0.1 µ timescale. By systematically simulating both homo- and heterocoalescence reactions, we identify a hierarchical reaction network in which ligand dynamics, transient metal exposure, and geometric compatibility jointly govern selection of fusion pathways. Generating and analyzing 87 distinct coalescence products, we identify size-dependent fusion behaviors and ligand-gated reactive windows that govern hierarchical cluster growth. Quantitative comparison with experimentally identified metal-ligand stoichiometries validates that our simulations reproduce experimentally observed surface-to-volume scaling laws and ligand coverage trends spanning more than a 20-fold range of cluster sizes. The robustness of these predictions is demonstrated through statistical analysis of reaction trajectories and structural motif evolution. Our strategy can be generalized to other ligand-protected metal nanoclusters and nanoparticle systems, provided sufficient training data is generated, offering a predictive framework for rational design of size-focused synthesis, controlled aggregation, and hierarchical assembly in nanocluster-based materials.

The fabrication of monodisperse microgels has achieved considerable success and has transformed many fields. However, conventional methods typically rely on external shear forces, interfacial perturbations, or toxic solvents, which restrict their application flexibility. This study presents a novel magnetic-field-actuated strategy for fabricating uniform microgels (300-900 µm) with tunable morphologies, including microspheres and microfibers, bypassing the need for external shear forces, interfacial perturbations, or toxic solvents. By integrating superparamagnetic iron oxide nanoparticles (SPIONs) into hydrogel precursors, internal magnetic stress gradients induce self-driven droplet segmentation, enabling precise control over particle size and structure with high-throughput production and exceptional uniformity. These biocompatible microgels exhibit robust magnetic responsiveness, facilitating precise positioning and occlusion in vascular embolism models and enhancing toxin clearance in hemodialysis by three to four times through turbulence induced by magnetically driven rotation. This magnetically programmable platform merges microgel synthesis and functionalization, offering a versatile class of carriers with adaptable structures for regenerative medicine and precision medicine applications.

Chirality-dependent optoelectronics and biological interactions have both attracted significant attention over the past several decades. However, interdisciplinary synergy between these two fields remains limited, largely due to the lack of theoretical support and practical demonstrations. Herein, we report the fabrication of biomolecule-tailored chiral PbS films via a solid-state ligand exchange method, enabling the achievement of a maximum chiroptical anisotropic factor (g-factor) of 2.36 × 10⁻³. These chiral PbS films were integrated into circularly polarized short-wave infrared (CP-SWIR) photodetectors, exhibiting a high responsivity beyond 0.3 A/W and a detectivity beyond 8.6 × 10¹¹ Jones under the irradiation (L-PbS film under left-handed CP-SWIR). More importantly, such chirality-mediated phenomenon enables antibacterial activity through a photo-microcurrent generation effect. It eventually provides a significant 39% difference in E. coli mortality rate when the L-PbS-based photosensitive device is subject to homochiral versus heterochiral CP-SWIR illumination. This strategy offers a robust platform for cross-collaborations between chiroptical optoelectronic devices and chirality-related biological issues.

Integrating bacteria with synthetic materials to construct biohybrid systems is an emerging strategy for developing functional living materials. In contrast to static covalent conjugation, engineering bacterial surfaces with supramolecular approaches offers reversible, modular, and dynamic control. In this study, we developed a robust cucurbit[7]uril-based supramolecular platform installed on the surface of bacteria, enabling the “plug-and-play” construction of functional biohybrids through host-guest interactions. This versatile strategy maintains bacterial integrity while allowing reversible and tunable surface modification. Using this platform, we successfully prepared functional biohybrids for diverse biomedical applications, including fluorescence imaging, drug delivery, and bioorthogonal catalysis, demonstrating its modularity and broad applicability. Notably, tumor-targeting bacteria equipped with catalytic modules achieved in situ synthesis of proteolysis-targeting chimeras (PROTACs) within the tumor microenvironment, leading to targeted protein degradation and significant tumor suppression in vivo, highlighting their potential for precision cancer therapy.