Photo-Facilitated Nitric Oxide-Triggered Turn-on Photodynamic Therapy for Precise Antitumor Application.

Photodynamic therapy (PDT) is a powerful strategy for tumor therapy with noninvasiveness and desirable efficacy. However, the phototoxicity of photosensitizer after the post-PDT is the major obstacle limiting the clinic applications. Herein, a nitric oxide (NO)-activatable photosensitizer is reported with turn-on PDT behavior and endoplasmic reticulum (ER) targeting ability for precise tumor therapy.

Facile Access to Phosphorus Ylide-fused Heteroarenes Possessing Tunable Optoelectronic Properties and High Nonlinear Optical Performances.

We report here a novel family of ylidic P-heteroarenes (P1-P6), structurally featuring unique phosphonium cyclopentadienylide (P-Cp)-fused π-skeletons and synthetically prepared via an unexpected one-pot [2+3]/[3+3] phospha-annulation reaction. While the facile and modular synthesis allows the fine-tuning of their optical absorptions and redox properties, single-crystallographic and theoretical analysis of these P-heteroarenes further reveal that the fusion of P-Cp moiety leads to substantial intramolecular charge-separated features with high ylidic character values of up to 84 %. Benefitted from such dipolar structures, these P-heteroarenes not only allows stepwise electrophilic substitution reaction for further structural π-expansions, but also exhibit excellent nonlinear optical (NLO) responses and optical limiting (OL) performances comparable to or exceed those of C.

Design and Construction of Highly Luminescent Transparent Woody Materials Exhibiting Unique Fluorescence-Enhanced Staining Effects for Visualization of Intrinsic Microporous Networks.

Luminescent wood materials are an emerging class of biomass hybrid host materials owing to the hierarchical porous structure and functionalization versatility. The fluorescence properties are largely dependent on exogenous fluorophores, which are, however, often plagued by notorious aggregation effects. In this work, an efficient strategy for the preparation of luminescent transparent wood materials is developed by incorporating tetraphenylethylene-derived aggregation-induced emission (AIE)-active fluorophores during a delignification-backfill transparency process.

Mesoscale Acid-Base Complexes Display Size-Associated Photophysical Property and Photochemical Activity.

The properties of single molecules and molecular aggregates can differ dramatically, leading to a long-standing interest in mesoscale aggregation processes. Herein, a series of acid-base molecular complexes is developed by using a tetraphenylethylene-backboned fluorophore, and investigated the photophysical properties and photochemical activities at different aggregation length scales. This fluorophore, with two basic diethylamine groups and two acidic tetrazole groups, exhibits sparse solubility due to multivalent interactions that cause infinite aggregation.

Unique Fluorescence of Aggregation-Induced Emission Luminogens on Solid Surfaces Modified by Silicone Nanofilaments.

Aggregation-induced emission (AIE) has revolutionized solid-state fluorescence by overcoming the limitations of aggregation-caused quenching. While extensively studied in solutions, AIE's potential on solid surfaces remains largely unexplored, which can be fundamentally interesting and practically useful. In this work, we demonstrate the successful dispersion of tetraphenylethylene (TPE), one of the most classical AIE luminogens, on solid surfaces coated with silicone nanofilaments (SNF).

Fluorogenic in-situ Labelling of Gelatin Polymer in Aqueous Solution and Hydrogel.

Gelatin polymers made from partially degraded collagen are important biomaterials, but their in-situ analysis suffers from uncontrollable covalent labelling and poor spatial-temporal imaging resolution. Herein, three tetrazolate-tagged tetraphenylethylene fluorophores (TPE-TAs) are introduced for practical fluorogenic labelling of gelatin in aqueous phase and hydrogels. These probes with aggregation-induced emission characteristics offer negligible background and elicit turn-on fluorescence by simply mixing with the gelatin in aqueous phase, giving a detection limit of 0.

Sulfone-Functionalized Chichibabin's Hydrocarbons: Stable Diradicaloids with Symmetry Breaking Charge Transfer Contributing to NIR Emission beyond 900 nm.

While monoradical emitters have emerged as a new route toward efficient organic light-emitting diodes, the luminescence property of organic diradicaloids is still scarcely explored. Herein, by devising a novel radical-radical coupling-based synthetic approach, we report a new class of sulfone-functionalized Chichibabin's hydrocarbon derivatives, , featuring varied substituent patterns and moderate to high diradical characters of 0.44-0.

/-Octa-substituted Perylene: A Versatile Building Block toward Novel Polycyclic (Hetero)Aromatic Hydrocarbons.

ConspectusPolycyclic (hetero)aromatic hydrocarbons (PAHs) have emerged as a focal point in current interdisciplinary research, spanning the realms of chemistry, physics, and materials science. Possessing distinctive optical, electronic, and magnetic properties, these π-functional materials exhibit significant potential across diverse applications, including molecular electronic devices, organic spintronics, and biomedical functions, among others. Despite the extensive documentation of various PAHs over the decades, the efficient and precise synthesis of π-extended PAHs remains a formidable challenge, hindering their broader application.

A Photoelectromagnetic 3D Metal-Organic Framework from Flexible Tetraarylethylene-Backboned Ligand and Dynamic Copper-Based Coordination Chemistry.

Porous frameworks that display dynamic responsiveness are of interest in the fields of smart materials, information technology, etc. In this work, a novel copper-based dynamic metal-organic framework [CuTTBPE(HO)] (HTTBPE = 1,1,2,2-tetrakis(4″-(1H-tetrazol-5-yl)-[1,1″-biphenyl]-4-yl)ethane), denoted as HNU-1, is reported which exhibits modulable photoelectromagnetic properties. Due to the synergetic effect of flexible tetraarylethylene-backboned ligands and diverse copper-tetrazole coordination chemistries, a complex 3D tunneling network is established in this MOF by the layer-by-layer staggered assembly of triplicate monolayers, showing a porosity of 59%.

Magnetic Bistability in an Organic Radical-Based Charge Transfer Cocrystal.

We report herein an organic charge transfer cocrystal complex, consisting of a stable radical and an electron acceptor , as a rare sort of all-organic-based magnetic bistable materials with a thermally activated magnetic hysteresis loop over the temperature range from 170 to 260 K. Detailed X-ray crystallographic studies and theoretical calculations revealed that while a π-associated radical anion dimer was formed upon an integer charge transfer process from to the molecules within the cocrystal lattice, the resulting π-dimers were found to exhibit varied intradimer π-stacking distances and singly occupied molecular orbital overlaps at different temperatures, thus yielding two different singlet states with distinct singlet-triplet gaps above and below the loop, which eventually contributed to the thermally excited molecular magnetic bistability.

α-Cyano Triaryl[3]radialene: Unsymmetrical Stereo-configuration, Clustering-enhanced Excimer Emission, and Radical-involved Multimodal Information Switching.

[3]Radialene has a peculiar topology and cross-conjugation system, representing a unique molecular scaffold in organic materials. Herein, we report a special class of stereoisomeric α-cyano triaryl[3]radialenes (CTRs) that show concentration-caused quenching in solution but emit red-shifted and enhanced luminescence in the crystalline state. Clustering of multiple cyano groups and their through-space interactions with the [3]radialene ring significantly extend π-electron communication meanwhile rigidifying the propeller conformation multivalently, thus playing a key role behind the state-dependent luminescence.

Dual Charge Transfer Generated from Stable Mixed-Valence Radical Crystals for Boosting Solar-to-Thermal Conversion.

Realizing dual charge transfer (CT) based on stable organic radicals in one system is a long-sought goal, however, remains challenging. In this work, a stable mixed-valence radical crystal is designed via a surfactant-assisted method, namely TTF-(TTF ) -RC (where TTF = tetrathiafulvalene), containing dual CT interactions. The solubilization of surfactants enables successful co-crystallization of mixed-valence TTF molecules with different polarity in aqueous solutions.

Fully-fused boron-doped olympicenes: modular synthesis, tunable optoelectronic properties, and one-electron reduction.

We report here a novel family of boraolympicenes, structurally featuring boron-doping at the concave 11a-position of their π-skeletons and synthetically prepared a facile one-pot triply borylation-based double-fold borocyclization reaction. Despite having no bulky protecting groups, these boraolympicenes exhibit excellent chemical stability against air and moisture, ascribed to the significant π-electron delocalization over the vacant p orbitals of boron atoms as evidenced by both single-crystallographic and theoretical analyses. More importantly, the modular synthesis of these boraolympicenes allows the fine-tuning of their physicochemical properties, endowing them with intriguing electronic features, such as intense visible-to-NIR absorption and low-lying LUMO energy levels (∼-3.

-region O-annulation of arylene diimide enables ambipolar transport of a polycyclic aromatic hydrocarbon with strong NIR absorption.

While the heteroannulation of arylene diimides serves as a powerful approach for designing new π-functional materials, most of the heteroannulated arylene diimides are constructed based on π-extension at their -areas or -directions. Herein, based on a -region O-annulation strategy, a novel O-doped polyaromatic hydrocarbon O-ADA was successfully prepared, showing not only ambipolar charge transport with improved charge mobilities, but also much red-shifted NIR absorption profiles and thus yielding enhanced photothermal conversion efficiencies upon light irradiation as compared to its parent ADA compound.

Photoelectromagnetic Responsive Adaptive Porous Frameworks through Dynamic Covalent Chemistry of Tetraarylethylene-backboned Aryldicyanomethyl Radicals.

Dynamic materials undergoing adaptive solid-state transitions are attractive for soft mechanics and information technology. Here, we report a novel porous framework system based on macrocyclic trimers assembled from open-shell tetraarylethylene building blocks with aryldicyanomethyl radicals as coupling linkers. Under mechanical, thermal, or chemical stimuli, the framework showed adaptability by activating conformational dynamics and radical-based transformations, thus displaying macroscopic responsiveness in terms of light absorption, luminescence, and magnetism.

A Methodology of Fabricating Novel Electrodes for Semiconductor Devices: Doping and Van der Waals Integrating Organic Semiconductor Films.

Electrodes are indispensable components in semiconductor devices, and now are mainly made from metals, which are convenient for use but not ideal for emerging technologies such as bioelectronics, flexible electronics, or transparent electronics. Here the methodology of fabricating novel electrodes for semiconductor devices using organic semiconductors (OSCs) is proposed and demonstrated. It is shown that polymer semiconductors can be heavily p- or n-doped to achieve sufficiently high conductivity for electrodes.

Novel Organic Superbase Dopants for Ultraefficient N-Doping of Organic Semiconductors.

Doping is a powerful technique for engineering the electrical properties of organic semiconductors (OSCs), yet efficient n-doping of OSCs remains a central challenge. Herein, the discovery of two organic superbase dopants, namely P2-t-Bu and P4-t-Bu as ultra-efficient n-dopants for OSCs is reported. Typical n-type semiconductors such as N2200 and PC BM are shown to experience a significant increase of conductivity upon doping by the two dopants.

Aggregation Effect on Multiperformance Improvement in Aryl-Armed Phenazine-Based Emitters.

The concept of aggregate science was proposed to explain changes in materials performance that accompany the generation of aggregates, but aggregation-triggered multifunction improvements in a class of materials have rarely been reported. Herein, we present the first report of a new class of multifunctional aggregation-induced emission (AIE) luminogens (AIEgens) based on 5,10-diarylphenazine (DPZ) derivates with full-wavelength emission. Intriguingly, multiple properties, such as fluorescence intensity and free radical and type I reactive oxygen species (ROS) efficiencies, could be simultaneously activated from the unimolecular level to the aggregate state.

Protocol for doping of an Sn-based two-dimensional perovskite semiconductor by incorporating SnI for field-effect transistors and thermoelectric devices.

Doping is an important technique for semiconductor materials, yet effective and controllable doping of organic-inorganic halide perovskites is still a challenge. Here, we present a protocol to dope 2D perovskite (PEA)SnI by incorporating SnI in the precursor solutions. We detail steps for preparation of field-effect transistors (FETs) and thermoelectric devices (TEs) based on SnI-doped (PEA)SnI films.

Ir(III) Complexes with AIE Characteristics for Biological Applications.

Both biological process detection and disease diagnosis on the basis of luminescence technology can provide comprehensive insights into the mechanisms of life and disease pathogenesis and also accurately guide therapeutics. As a family of prominent luminescent materials, Ir(III) complexes with aggregation-induced emission (AIE) tendency have been recently explored at a tremendous pace for biological applications, by virtue of their various distinct advantages, such as great stability in biological media, excellent fluorescence properties and distinctive photosensitizing features. Significant breakthroughs of AIE-active Ir(III) complexes have been achieved in the past few years and great progress has been witnessed in the construction of novel AIE-active Ir(III) complexes and their applications in organelle-specific targeting imaging, multiphoton imaging, biomarker-responsive bioimaging, as well as theranostics.

Furan-Extended Helical Rylenes with Fjord Edge Topology and Tunable Optoelectronic Properties.

Lateral furan-expansion of polycyclic aromatics, which enables multiple O-doping and peripheral edge evolution of rylenes, is developed for the first time. Tetrafuranylperylene TPF-4CN and octafuranylquaterrylene OFQ-8CN were prepared as model compounds bearing unique fjord edge topology and helical conformations. Compared to TPF-4CN, the higher congener OFQ-8CN displays a largely red-shifted (≈333 nm) and intensified absorption band (λ =829 nm) as well as a narrowed electrochemical band gap (≈1.

Revealing the Electrophilic-Attack Doping Mechanism for Efficient and Universal p-Doping of Organic Semiconductors.

Doping is of great importance to tailor the electrical properties of semiconductors. However, the present doping methodologies for organic semiconductors (OSCs) are either inefficient or can only apply to some OSCs conditionally, seriously limiting their general applications. Herein, a novel p-doping mechanism is revealed by investigating the interactions between the dopant trityl tetrakis(pentafluorophenyl) borate (TrTPFB) and poly(3-hexylthiophene) (P3HT).

A nonconjugated radical polymer with stable red luminescence in the solid state.

Organic radicals are unstable and stable radicals usually display non-luminescent properties. Luminescent radicals possess the all-in-one properties of optoelectronics, electronics, and magnetics. To date, the reported structures of luminescent radicals are limited to triphenylmethyl radical derivatives and their analogues, which are stabilized with extended π-conjugation.

Doping of Sn-based two-dimensional perovskite semiconductor for high-performance field-effect transistors and thermoelectric devices.

Doping is an important technique for semiconductor materials and devices, yet effective and controllable doping of organic-inorganic halide perovskites is still a challenge. Here, we demonstrate a facile way to dope two-dimensional Sn-based perovskite (PEA)SnI by incorporating SnI in the precursor solutions. It is observed that Sn produces p-doping effect on the perovskite, which increases the electrical conductivity by 10 times.

Perylene-Based Linear Nonalternant Nanoribbons with Bright Emission and Ambipolar Redox Behavior.

Here we report stepwise solution-synthesis of linear nonalternant nanoribbons (NNRs), featuring pentagonal rings peri-fused onto the repeating perylene unit. The X-ray single-crystal structures demonstrated their π-backbones as a twisted ribbon, with the longest crystalline length of the nanoribbon up to 3.9 nm.