Long-lived Emission Research Articles

Buckling cluster-based H-bonded icosahedral capsules and their propagation to a robust zeolite-like supramolecular framework

Hydrogen-bonded assembly of multiple components into well-defined icosahedral capsules akin to virus capsids has been elusive. In parallel, constructing robust zeolitic-like cluster-based supramolecular frameworks (CSFs) without any coordination covalent bonding linkages remains challenging. Herein, we report a cluster-based pseudoicosahedral H-bonded capsule Cu60, which is buckled by the self-organization of judiciously designed constituent copper clusters and anions. The spontaneous formation of the icosahedron in the solid state takes advantage of 48 charge-assisted CH···F hydrogen bonds between cationic clusters and anions (PF6-), and is highly sensitive to the surface protective ligands on the clusters with minor structural modification inhibiting its formation. Most excitingly, an extended three-periodic robust zeolitic-like CSF, is constructed by edge-sharing the resultant icosahedrons. The perpendicular channels of the CSF feature unusual 3D orthogonal double-helical patterns. The CSF material not only keeps its single-crystal character in the desolvated phase, but also exhibits excellent chemical and thermal stabilities as well as long-lived phosphorescence emission.

Recent Advances in Thermally Activated Delayed Fluorescence-Based Organic Afterglow Materials.

Thermally activated delayed fluorescence (TADF)-based materials are attracting widespread attention for different applications owing to their ability of harvesting both singlet and triplet excitons without noble metals in their structures. As compared to the conventional fluorescence and room-temperature phosphorescence pathways, TADF originates from the reverse intersystem crossing process from the excited triplet state (T1) to the singlet state (S1). Therefore, TADF emitters enabling activated and long lifetime T1 excitons are potential candidates for generating long-lived afterglow emission, an effect that can still be observed for a while by the naked eye after the removal of the excitation light source. Recently, TADF-based organic afterglow materials featuring high photoluminescence quantum yields and long lifetimes above 100 ms under ambient conditions, have emerged for advanced information security, high-contrast biological imaging, optoelectronic devices, and intelligent sensors, whereas the related systematic review is still lacking. Herein, the recent progress in TADF-based organic afterglow materials is summarized and an overview of the photophysical mechanism, design strategies, and the performances for relevant applications is given. In addition, the challenge and perspective of this area are given at the end of the review.

Controlled Photooxidation via Singlet Oxygen Generation by Triplet Harvesting in a Heavy Atom Free Pure Organic Dithienylethene-Naphthalene Diimide.

Noninvasive control over the reversible generation of singlet oxygen (1O2) has found the enormous practical implications in the field of biomedical science. However, metal-free pure organic emitters, connected with a photoswitch, capable of generating "on-demand" 1O2 via triplet harvesting remain exceedingly rare; therefore, the utilization of these organic materials for the reversible control of singlet oxygen production remains at its infancy. Herein, an ambient triplet mediated emission in quinoline-dithienylethene (DTE)-core-substituted naphthalene diimide (cNDI) derivative is unveiled via delayed fluorescence. The quinoline-DTE-cNDI triad displayed enhanced photoswitching efficiency via double FRET mechanism. It was found to have direct utilization in controlled photosensitized organic transformations via efficient generation of singlet oxygen (yield ΦΔ~0.55 in DCM and 0.73 in methanol). The designed molecule exhibits a long-lived emission (τ∼1.1 μs) and very small singlet-triplet splitting (ΔEST) of 0.13 eV empowering it to display delayed fluorescence. Comprehensive steady state and time-resolved emission spectroscopy (TRES) analyses along with DFT calculations offer detailed understandings into the excited-state manifolds of organic compound and energy transfer (ET) pathways involved in 1O2 generation.

Tunable Interlayer Interactions in Exfoliated 2D van der Waals Framework Fe(SCN)2(Pyrazine)2.

2D materials can be isolated as monolayer sheets when interlayer interactions involve weak van der Waals forces. These atomically thin structures enable novel topological physics and open chemical questions of how to tune the structure and properties of the sheets while maintaining them as isolated monolayers. Here, this work investigates 2D electroactive sheets that exfoliate in solution into colloidal nanosheets, but aggregate upon oxidation, giving rise to tunable interlayer charge transfer absorption and photoluminescence. This optical behavior resembles interlayer excitons, now intensely studied due to their long-lived emission, but which remain difficult to tune through synthetic chemistry. Instead, the interlayer excitons of these framework sheets can be modulated through control of solvent, electrolyte, oxidation state, and the composition of the framework building blocks. Compared to other 2D materials, these framework sheets display the largest known interlayer binding strengths, attributable to specific orbital interactions between the sheets, and among the longest interlayer exciton lifetimes. Taken together, this study provides a microscopic basis for manipulating long-range opto-electronic behavior in van der Waals materials through molecular synthetic chemistry.

On the glow of cremated remains: long-lived green photo-luminescence of heat-treated human bones.

The long-lived green luminescence of human bone (that has been heated to 600°C for a short duration) is attributed to a carbon quantum dot material (derived from collagen) encapsulated and protected by an inorganic matrix (derived from bone apatite) and is more intense in dense rigid and crystalline parts of (healthy) human bones. The strong collagen-apatite interaction results (upon decomposition) in a protective inorganic environment of the luminescent centers allowing long-lived triplet-based emission of a carbon (quantum) dot-like material at room temperature, as well as resilience against oxidation between 550 and 650°C. The graphitic black phase (obtained upon heating around 400°C) is a precursor to the luminescent carbon-based material, that is strongly interacting with the crystalline inorganic matrix. Human bone samples that have been heated to 600°C were subjected to steady-state and time-resolved spectroscopy. Excitation-emission matrix (EEM) luminescence spectroscopy revealed a broad range of excitation and emission wavelengths, indicating a heterogeneous system with a broad density of emissive states. The effect of low temperature on the heat-treated bone was studied with Cryogenic Steady State Luminescence Spectroscopy. Cooling the bone to 80K leads to a slight increase in total emission intensity as well as an intensity increase towards to red part of the spectrum, incompatible with a defect state model displaying luminescent charge recombination in the inorganic matrix. Time-resolved spectroscopy with an Optical Multichannel Analyzer (OMA) and Time Correlated Single Photon Counting (TCSPC) of these samples showed that the decay could be fitted with a multi-exponential decay model as well as with second-order decay kinetics. Confocal Microscopy revealed distinct (plywood type) structures in the bone and high intensity-fast decay areas as well as a spatially heterogeneous distribution of green and (fewer) red emissive species. The use of the ATTO 565 dye aided in bone-structure visualization by chemical adsorption. Conceptually our data interpretation corresponds to previous reports from the material science field on luminescent powders.

Achieving Near-Infrared Phosphorescence Supramolecular Hydrogel Based on Amphiphilic Bromonaphthalimide Pyridinium Hierarchical Assembly.

Phosphorescent supramolecular hydrogels are currently a prevalent topic for their great promise in various photonic applications. Herein, an efficient near-infrared (NIR) phosphorescence supramolecular hydrogel is reported via the hierarchical assembly strategy in aqueous solution, which is fabricated from amphiphilic bromonaphthalimide pyridinium derivative (G), exfoliated Laponite (LP) nanosheets, and polymeric polyacrylamide (PAAm). Initially, G spontaneously self-aggregates into spherical nanoparticles covered with positively charged pyridinium units and emits single fluorescence at 410nm. Driven by electrostatic interactions with negatively charged nanosheets, the nanoparticles subsequently function as the cross-linked binders and coassemble with LP into supramolecular hydrogels with an engendered red room-temperature phosphorescence (RTP) up to 620nm. Benefiting from hydrogen-bonding interactions-mediated physical cross-linkage, the further introduction of PAAm not only significantly elevates the mechanical strength of the hydrogels showing fast self-healing capability, but also increases phosphorescence lifetime from 2.49to 4.20ms, especially generating phosphorescence at even higher temperature (τ 363 K = 2.46ms). Additionally, efficient RTP energy transfer occurs after doping a small amount of organic dye heptamethine cyanine (IR780) as an acceptor into hydrogels, resulting in a long-lived NIR emission at 823nm with a high donor/acceptor ratio, which is successfully applied for cell labeling in the NIR window.

Dual Luminescent Mn(II)-Doped Cu-In-Zn-S Quantum Dots as Temperature Sensors in Water.

CuInS2 quantum dots have emerged in the last years as non-toxic alternative to traditional Pb and Cd based quantum dots, especially for biological applications. In this work, the hydrothermal synthesis of alloyed Cu-In-Zn-S quantum dots (CIZS) doped with manganese(II) is explored, with different metal ratios (Mn-CIZSy). The doped quantum dots show the sensitized emission of Mn2+ (approximately ms lifetime), together with the emission of the CIZS structure (approximately µs lifetime). The relative contribution of Mn2+ emission is highly dependent on the composition of the CIZS hosting structure (In:Cu ratio). In addition to that, it is shown that Mn2+ sensitization requires a threshold energy, which suggests the involvement of an intermediate state in the sensitization mechanism. The long-lived emission intensity decay of Mn2+ shows a stable and reversible temperature response in physiological conditions (25-45°C, pH = 7.4). Mn-CIZSy quantum dots are thus interesting candidates as biological luminescent temperature probe thanks to their easy synthesis, high colloidal stability, insensitivity to dioxygen quenching and quantitative time-gated detection.

Organelle-Targeting Polymer Dots Exhibiting Thermally Activated Delayed Fluorescence for Subcellular Imaging.

Selective imaging of specific subcellular structures provides valuable information about the cellular microenvironment. Materials exhibiting thermally activated delayed fluorescence (TADF) are rapidly emerging as metal-free probes with long-lived emission for intracellular time-gated imaging applications. Polymers incorporating TADF emitters can self-assemble into luminescent nanoparticles, termed polymer dots (Pdots), and this strategy enables them to circumvent the limitations of commercial organelle trackers and small molecule TADF emitters. In this study, diblock copolymers comprised of a hydrophilic block containing organelle-targeting monomers and a hydrophobic TADF-active block were synthesized by ring-opening metathesis polymerization (ROMP). Oxanorbornene-based monomers incorporating morpholine and triphenylphosphonium groups for lysosome and mitochondria targeting, respectively, were also synthesized. ROMP by sequential addition yielded well-defined diblock copolymers with dispersities <1.28. To analyze the effect of tuning the hydrophilic corona on cellular viability and uptake, we prepared Pdots with poly(ethylene glycol) (PEG) and bis-guanidinium (BGN) coronas, resulting in limited and efficient cellular uptake, respectively. Red-emissive Pdots with BGN-based coronas and organelle-targeting functionality were obtained with quantum yields up to 12% in water under air. Colocalization analysis confirmed that lysosome and mitochondria labeling in live HeLa cells was accomplished within 2 h of incubation, affording Pearson's correlation coefficients of 0.37 and 0.70, respectively. The potential application of these Pdots for time-resolved imaging is highlighted by a proof of concept using time-gated spectroscopy, which effectively separates the delayed emission of the TADF Pdots from the background autofluorescence of biological serum.

Efficient Microwave Irradiation-Assisted Synthesis of Benzodioxinoquinoxaline and Its Donor-Variegated Derivatives Enabling Long-Lived Emission and Efficient Bipolar Charge Carrier Transport

Efficient Microwave Irradiation-Assisted Synthesis of Benzodioxinoquinoxaline and Its Donor-Variegated Derivatives Enabling Long-Lived Emission and Efficient Bipolar Charge Carrier Transport

Mixed-Layered Lead Halide Frameworks with High Stability and Efficient Room-Temperature Phosphorescence.

Room-temperature phosphorescent (RTP) materials play a crucial role in optical anticounterfeiting science and information security technologies. Ionically bonded organic metal halides have emerged as promising RTP material systems due to their excellent self-assembly and unique photophysical property, but their intrinsic instability largely hinders their advanced practical applications. Herein, we employ a coordination-driven synthetic strategy utilizing organocarboxylates for the synthesis of two isostructural layered lead halide frameworks. The frameworks adopt a new mixed-layered topology, consisting of alternating [Pb10X9]11+ (X = Cl-/Br-) layers and [Pb6XO3]11+ (X = Cl-/Br-) layers that are coordinatively sandwiched by organocarboxylate layers. The frameworks exhibit long-lived green afterglow emission with the long lifetime of up to 45.89 ms and the photoluminescence quantum yield (PLQY) of up to 43.13%. The Pb2+-carboxylate coordination accelerates the metal-to-ligand charge transfer from the light-harvesting lead halide layers to the phosphorescent organic component, promoting efficient spin-orbit coupling and intersystem crossing. Moreover, the coordination networks exhibit good structural robustness under ambient conditions for at least 12 months, as well as stability in boiling water, acidic and basic aqueous environments. The highly efficient afterglow and high structural integrity enable multiple anticounterfeiting applications across diverse chemical environments.

Fluorescence Screening of DNA-AgNCs with Pulsed White Light Excitation.

DNA-stabilized silver nanoclusters (DNA-AgNCs) are a class of fluorophores with interesting photophysical properties dominated by the choice of DNA sequence. Screening methods with ultraviolet excitation and steady state well plate readers have previously been used for deepening the understanding between DNA sequence and emission color of the resulting DNA-AgNCs. Here, we present a new method for screening DNA-AgNCs by using pulsed white light excitation (λex ≈ 490-900 nm). By subtraction and time gating we are able to circumvent the dominating scatter of the white excitation light and extract both temporally and spectrally resolved emission of DNA-AgNCs over the visible to near-infrared range. Additionally, we are able to identify weak long-lived emission, which is often buried underneath the intense nanosecond fluorescence. This new approach will be useful for future screening of DNA-AgNCs (or other novel emissive materials) and aid machine-learning models by providing a richer training data set.

Author Correction: Unveiling long-lived dual emission in a tetraphenylethylene-based metal–organic framework

Author Correction: Unveiling long-lived dual emission in a tetraphenylethylene-based metal–organic framework

Highly Stable MOF-Type Lead Halide Luminescent Ferroelectrics.

Lead halide molecular ferroelectrics represent an important class of luminescent ferroelectrics, distinguished by their high chemical and structural tunability, excellent processability and distinctive luminescent characteristics. However, their inherent instability, prone to decomposition upon exposure to moisture and light, hinders their broader ferroelectric applications. Herein, for the first time, we present a series of isoreticular metal-organic framework (MOF)-type lead halide luminescent ferroelectrics, demonstrating exceptional robustness under ambient conditions for at least 15 months and even when subjected to aqueous boiling conditions. Unlike conventional metal-oxo secondary building units (SBUs) in MOFs adopting highly centrosymmetric structure with limited structural distortion, our lead halide-based MOFs occupy structurally deformable [Pb2X]+ (X=Cl-/Br-/I-) SBUs that facilitate a c-axis-biased displacement of Pb2+ centers and substantially contribute to thermoinducible structural transformation. Importantly, this class of MOF-type lead halide ferroelectrics undergo ferroelectric-to-paraelectric phase transitions with remarkably high Curie temperature of up to 505 K, superior to most of molecular ferroelectrics. Moreover, the covalent bonding between phosphorescent organic component and the light-harvesting inorganic component achieves efficient spin-orbit coupling and intersystem crossing, resulting in long-lived afterglow emission. The compelling combination of high stability, ferroelectricity and afterglow emission exhibited by lead halide MOFs opens up many potential opportunities in energy-conversion applications.

Unveiling long-lived dual emission in a tetraphenylethylene-based metal–organic framework

Unveiling long-lived dual emission in a tetraphenylethylene-based metal–organic framework

Stretchable phosphorescent polymers by multiphase engineering

Stretchable phosphorescence materials potentially enable applications in diverse advanced fields in wearable electronics. However, achieving room-temperature phosphorescence materials simultaneously featuring long-lived emission and good stretchability is challenging because it is hard to balance the rigidity and flexibility in the same polymer. Here we present a multiphase engineering for obtaining stretchable phosphorescent materials by combining stiffness and softness simultaneously in well-designed block copolymers. Due to the microphase separation, copolymers demonstrate an intrinsic stretchability of 712%, maintaining an ultralong phosphorescence lifetime of up to 981.11 ms. This multiphase engineering is generally applicable to a series of binary and ternary initiator systems with color-tunable phosphorescence in the visible range. Moreover, these copolymers enable multi-level volumetric data encryption and stretchable afterglow display. This work provides a fundamental understanding of the nanostructures and material properties for designing stretchable materials and extends the potential of phosphorescence polymers.

Structural Optimization of BODIPY Derivatives: Achieving Stable and Long-Lived Green Emission in Hyperfluorescent OLEDs.

Boron dipyrromethene (BODIPY) derivatives are widely studied as terminal emitters in organic light-emitting diodes (OLED) due to their narrow emission and high photoluminescence quantum yield (PLQY). However, the strategy for precisely tuning their emission toward a high color purity is still challenging. Herein, we developed a new design strategy to regulate the emission of BODIPY derivatives by modifying the electronic and steric dominance using functionalities, such as nitrile, pentafluorophenyl, diethyl, and monobenzyl. These rational modifications yielded a series of four novel green BODIPY emitters, namely, tPN-BODIPY, tPPP-BODIPY, tPBn-BODIPY, and tPEN-BODIPY, each benefited with a tuned emissions range of 517 to 542 nm with a narrow fwhm of 25 nm and high photoluminescence quantum yield up to 96%. Among these synthesized BODIPYs, an unsymmetrical tPBn-BODIPY was chosen as a final dopant (FD) to explore its application in OLED devices. The fabricated TADF sensitized fluorescence-OLED (TSF-OLED) exhibits a narrow band pure green emission at 531 nm with corresponding CIE coordinates of (x, y) = (0.27, 0.68) and a maximum external quantum efficiency (EQE) of 20%. Furthermore, the TSF-OLED displayed an exceptionally prolonged device operational lifetime (LT90) of 210 h at an initial luminescence of 3000 cd m-2.

Tryptophan-Doped Poly(vinyl alcohol) Films with Ultralong-Lifetime Room-Temperature Phosphorescence and Color-Tunable Afterglow Under Ambient Conditions.

The development of a persistent luminescence system with long-lived phosphorescence and color-tunable afterglow at room temperature represents a challenge, largely due to the intensive non-radiative deactivation pathway. In this study, an ultralong-lived room temperature phosphorescence (RTP) system has been achieved using a hydrogen-bonding strategy where poly(vinyl alcohol) (PVA) matrices were doped with tryptophan (Trp) derivatives. The PVA film doped with N-α-(9-Fluorenylmethoxycarbonyl)-L-tryptophan (Fmoc-L-Trp) exhibited a long-lived phosphorescence emission of up to 3859.70 ms, and a blue afterglow for a duration greater than 34 s, under ambient conditions. The introduction of two other fluorescent dyes (i. e., Rhodamine B and Basicred14) to the PVA film facilitates adjustment to the color of the afterglow from blue to orange, and pink, by a triplet-to-singlet Förster-resonance energy transfer (TS-FRET) process. These films have been successfully applied in silk-screen printing and in multicolor afterglow light-emitting diode (LED) arrays.

A novel group of N,N-diaryl-1,2-benzenediamine room temperature phosphors based on structural engineering

Room temperature phosphorescence (RTP) has gained new momentum as a long-term topic along with the appearance of novel phosphors with versatile application potentials. Compared to traditional RTP materials, innovative pure organic phosphors have become promising alternatives due to their superiority in cost and processibility. However, the development of single-component organic phosphors with ultralong emission lifetimes and simple structures is still ongoing. Despite several kinds of organic phosphors being developed, the ones utilizing arylamine skeletons are barely reported. In this paper, we present a novel family of N,N-diaryl-1,2-benzenediamine phosphors with varying numbers of methyl substituents on terminal phenyl rings based on structural engineering. These molecules exhibited bright phosphorescence in the region of green to yellow light with a remarkably long lifetime up to 684 ms in crystalline states under ambient conditions. Comprehensive experimental and theoretical studies revealed that diverse intermolecular interactions and weak intramolecular hydrogen bonds co-contribute to the long-lived RTP emission. An encryption QR code was constructed, which displayed great potential in anti-counterfeiting applications. This work offered a novel structural motif for ultralong RTP material design and is constructive for material pool expansion.

Dual Optical Response Strategy for the Detection of Cytochrome c Using Highly Luminescent Lanthanide-Based Nanotubular Sensor Arrays.

Here, we demonstrate a label-free dual optical response strategy for the detection of cytochrome c (Cyt c) with ultrahigh sensitivity using highly luminescent lanthanides containing inorganic-organic hybrid nanotubular sensor arrays. These sensor arrays are formed by the sequential incorporation of the photosensitizers 2,3-dihydroxynaphthalene (DHN) or 1,10-phenanthroline (Phen), and trivalent lanthanide terbium ions (Tb3+) into sodium lithocholate (NaLC) nanotube templates. Our sensing platform relies on the detection and quantification of Cyt c in solution by providing dual photoluminescence quenching responses from the nanotubular hybrid arrays in the presence of Cyt c. The large quenching of the sensitized Tb3+ emission within the DHN/Phen-Tb3+-NaLC nanotubular sensor arrays caused by the strong binding of the photosensitizers to Cyt c provides an important signal response for the selective detection of Cyt c. This long-lived lanthanide emission response-based sensing strategy can be highly advantageous for the detection of Cyt c in a cellular environment eliminating background fluorescence and scattering signals through time-gated measurements. The DHN containing nanotubular sensor arrays (DHN-NaLC and DHN-Tb3+-NaLC) provide an additional quenching response characterized by a unique spectral valley splitting with quantized quenching dip on the DHN fluorescence emission. This spectral quenching dip resulting from efficient FRET between the protein bound DHN photosensitizer and the heme group of Cyt c serves as an important means for specific detection and quantification of Cyt c in the concentration range of 0-30 μM with a low detection limit of around 20 nM.

Employing phosphorescent carbon dots@silica for glutathione sensing with low background interference

Glutathione (GSH) has important physiological functions and has been implicated in several diseases. It is therefore of great physiological importance and clinical value to develop simple and efficient methods for measuring GSH levels. However, common used luminescent materials with short lifetimes inevitably generated background signal from the biological samples during light excitation. In this work, a GSH sensing method with ultralow background interference was developed using phosphorescent carbon dots (CDs). Introducing heteroatom and carbonyl group effectively activated the triplet state of phosphorescent CDs. Meanwhile, immobilization of CDs in SiO2 (CDs@SiO2) realized long-lived phosphorescent emission (lifetime of 1.54 s) in aqueous dispersion. Manganese dioxide (MnO2) quenched the phosphorescence of CDs@SiO2 via inner filter effect and triplet energy transfer, yet the phosphorescence was restored when GSH was present. The phosphorescence was recorded when the excitation source was turned off, which successfully eliminated the background fluorescence of biological samples. The work presented here will promote the fabrication of bioprobes with low background.