Strong Phosphorescence Research Articles

Dual Emission with Efficient Phosphorescence Promoted by Intermolecular Halogen Interactions in Luminescent Tetranuclear Zinc(II) Clusters.

The development of Zn-based phosphorescent materials, associated with a ligand-centered (LC) transition, is extremely limited. Herein, we demonstrated dual emissions including fluorescence and phosphorescence in luminescent tetranuclear Zn(II) clusters [Zn4LI4(μ3-OMe)2X2] (HLI = methyl-5-iode-3-methoxysalicylate; X = I, Br, Cl), incorporating iodine-substituted ligands. Single-crystal X-ray structural analyses and variable-temperature emission spectra studies revealed the presence of iodine substitutions, and intermolecular halogen interactions produced the internal/external heavy-atom effects and yielded strong green phosphorescence with a long emission lifetime (λmax = 510-522 nm, Φem = 0.28-0.47, τav = 0.78-0.95 ms, at 77 K). This work provided a new example that the introduction of halogen interactions is an advantageous approach for inducing phosphorescence in fluorescent metal complexes.

Influence of the atmosphere on the phosphorescence of a brominated diphenylphosphine oxide-ethyl naphthaleneimide dyad.

The molecular dyad diphenylphosphine-ethyl bromine naphthaleneimide (Br-DPPENI) emits strong fluorescence and phosphorescence. We studied the intensity and lifetime of the phosphorescence of Br-DPPENI embedded in PMMA films in atmospheres of air, He, Ar, N2, and O2 as a function of pressure between vacuum and ambient pressure (1 bar). The experiment was performed in the frequency domain with a two-channel lock-in amplifier, and the data were analyzed with the polar plot or phasor technique. Reversible shortening of the lifetime due to triplet-triplet annihilation was found in the presence of atmospheric or pure oxygen. With small modulation frequencies, an additional slow component of the phosphorescence dynamics is observed, which is ascribed to the diffusion of oxygen into the sample films.

Iridium(III)-Incorporating Self-Healing Polysiloxanes as Materials for Light-Emitting Oxygen Sensors.

Polymer-metal complexes (PMCs) based on poly(2,2'-bipyridine-4,4'-dicarboxamide-co-polydimethylsiloxanes) with cyclometalated di(2-phenylpyridinato-C2,N')iridium(III) fragments and cross-linked by Zn2+ (Zn[Ir]-BipyPDMSs) or Ir3+ (Ir[Ir]-BipyPDMSs) represent flexible, stretchable, phosphorescent, and self-healing molecular oxygen sensors. PMCs provide strong phosphorescence at λem = 595-605nm. Zn[Ir]-BipyPDMS with PDMS chain length of Mn = 5000 has the highest quantum yield of 9.3% and is a molecular oxygen sensor at different O2 concentrations (0-100vol%) compared to Ir[Ir]-BipyPDMSs. A Stern-Volmer constant is determined for Zn[Ir]-BipyPDMS as KSV = 0.014%-1, which is similar to the reported oxygen-sensitive iridium(III) complexes. All synthesized PMCs exhibit high elongation at break (up to 1100%) and self-healing efficiency (up to 99%).

Copper(I)‐Arsine Clusters with a Near‐Unity Phosphorescence Quantum Yield for X‐Ray Scintillation and LED Applications

AbstractRare‐earth element‐free materials that exhibit strong room temperature phosphorescence (RTP) and X‐ray scintillation properties are gaining global interest incessantly in the recent years. This work reports a series of easily synthesizable cubane Cu4I4‐triarsenic clusters [Cu4I4(R3As)3L] (L = none or nitrile), that exhibit a strong yellow‐green RTP with quantum efficiencies up to 100% and short decay times (4.4–4.9 µs). The title cluster complexes display X‐ray scintillation properties with a record ultralow detection limit (18.1 nGy s−1) and a perfectly linear dose rate response within a remarkably wide dose rate window (0–640 µGyair s−1). The cluster [Cu4I4(Ph3As)3] is highlighted as an efficient phosphor for UV‐pumped white and yellow LED devices, demonstrating an excellent white spectrum with a CIE index of (0.32,0.33) and bright yellow emission, respectively. These results may stimulate the future efforts in designing highly efficient arsenic‐based RTP materials and enriching the Cu4I4 cluster family.

Fluorescent, phosphorescent, magnetic resonance contrast and radioactive tracer labelling of extracellular vesicles.

This review focusses on the significance of fluorescent, phosphorescent labelling and tracking of extracellular vesicles (EVs) for unravelling their biology, pathophysiology, and potential diagnostic and therapeutic uses. Various labeling strategies, such as lipid membrane, surface protein, luminal, nucleic acid, radionuclide, quantum dot labels, and metal complex-based stains, are evaluated for visualizing and characterizing EVs. Direct labelling with fluorescent lipophilic dyes is simple but generally lacks specificity, while surface protein labelling offers selectivity but may affect EV-cell interactions. Luminal and nucleic acid labelling strategies have their own advantages and challenges. Each labelling approach has strengths and weaknesses, which require a suitable probe and technique based on research goals, but new tetranuclear polypyridylruthenium(II) complexes as phosphorescent probes have strong phosphorescence, selective staining, and stability. Future research should prioritize the design of novel fluorescent probes and labelling platforms that can significantly enhance the efficiency, accuracy, and specificity of EV labeling, while preserving their composition and functionality. It is crucial to reduce false positive signals and explore the potential of multimodal imaging techniques to gain comprehensive insights into EVs.

Insights into mechanistic interpretation of crystalline-state reddish phosphorescence of non-planar π-conjugated organoboron compounds.

Metal-free room-temperature phosphorescent (RTP) materials are attracting attention in such applications as organic light-emitting diodes and bioimaging. However, the chemical structures of RTP materials reported thus far are mostly predominantly based on π-conjugated systems incorporating heavy atoms such as bromine atoms or carbonyl groups, resulting in limited structural diversity. On the other hand, triarylboranes are known for their strong Lewis acidity and deep LUMO energy levels, but few studies have reported on their RTP properties. In this study, we discovered that compounds based on a tetracyclic structure containing boron, referred to as benzo[d]dithieno[b,f]borepins, exhibit strong solid-state reddish phosphorescence even in air. Quantum chemical calculations, including those for model compounds, revealed that the loss of planarity of the tetracyclic structure increases spin-orbit coupling matrix elements, thereby accelerating the intersystem crossing process. Moreover, single-crystal X-ray structural analysis and natural energy decomposition analysis suggested that the borepin compounds without bromine or oxygen atoms, unlike typical RTP materials, exhibit red-shifted phosphorescence in the crystalline state owing to structural relaxation in the T1 state. Additionally, the borepin compounds showed potential application as bioimaging dyes.

Enhanced solid-state phosphorescence of organoplatinum π-systems by ion-pairing assembly.

Anion binding and ion pairing of dipyrrolyldiketone PtII complexes as anion-responsive π-electronic molecules resulted in photophysical modulations, as observed in solid-state phosphorescence properties. Modifications to arylpyridine ligands in the PtII complexes significantly impacted the assembling behaviour and photophysical properties of anion-free and anion-binding (ion-pairing) forms. The PtII complexes, in the presence of guest anions and their countercations, formed various anion-binding modes and ion-pairing assembled structures depending on constituents and forms (solutions and crystals). The PtII complexes emitted strong phosphorescence in deoxygenated solutions but showed extremely weak phosphorescence in the solid state owing to self-association. In contrast, the solid-state ion-pairing assemblies with tetraalkylammonium cations exhibited enhanced phosphorescence owing to the formation of hydrogen-bonding 1D-chain PtII complexes dispersed by stacking with aliphatic cations. Theoretical studies revealed that the enhanced phosphorescence in the solid-state ion-pairing assembly was attributed to preventing the delocalisation of the electron wavefunction over PtII complexes.

Multi-resonance emitters with room-temperature phosphorescence in amorphous state and excited by visible light.

Unlike boron, nitrogen-containing multi-resonance emitters with thermally activated delayed fluorescence, here we report boron, sulfur (B, S)-based multi-resonance emitters with room-temperature phosphorescence (RTP) by inserting thiophene into a 5,9-dithia-13b-boranaphtho[3,2,1-de]anthracene skeleton that simultaneously realizes large singlet-triplet energy splitting and strong spin-orbital coupling, leading to efficient room-temperature phosphorescence in an amorphous state. Unlike most RTP emitters with ultraviolet excitation, the multi-resonance RTP emitters exhibit strong phosphorescence under daily-use blue/white LED lamps owing to their intense absorption in the visible-light region (400-486 nm). Meanwhile, such RTP behavior can be tuned by the number and fusing pattern of the thiophene moieties, with the emitters containing thiophene linked to boron atoms via α-positions exhibiting bathochromatically shifted emissions and longer phosphorescence lifetimes (47.7-119.4 ms) than those with β-position linkages. Given these features, amorphous RTP films with different emission colors and lifetimes are fabricated by dispersing the emitters in a poly(methyl methacrylate) matrix, and their applications in multi-color anti-counterfeiting are presented. These findings thus open a way to develop multi-resonance emitters as a new family of pure organic RTP materials that can work in an amorphous state and under visible-light excitation.

Layered rare-earth hydroxides as multi-modal medical imaging probes: particle size optimisation and compositional exploration.

Recently, layered rare-earth hydroxides (LRHs) have received growing attention in the field of theranostics. We have previously reported the hydrothermal synthesis of layered terbium hydroxide (LTbH), which exhibited high biocompatibility, reversible uptake of a range of model drugs, and release-sensitive phosphorescence. Despite these favourable properties, LTbH particles produced by the reported method suffered from poor size-uniformity (670 ± 564 nm), and are thus not suitable for therapeutic applications. To ameliorate this issue, we first derive an optimised hydrothermal synthesis method to generate LTbH particles with a high degree of homogeneity and reproducibility, within a size range appropriate for in vivo applications (152 ± 59 nm, n = 6). Subsequently, we apply this optimised method to synthesise a selected range of LRH materials (R = Pr, Nd, Gd, Dy, Er, Yb), four of which produced particles with an average size under 200 nm (Pr, Nd, Gd, and Dy) without the need for further optimisation. Finally, we incorporate Gd and Tb into LRHs in varying molar ratios (1 : 3, 1 : 1, and 3 : 1) and assess the combined magnetic relaxivity and phosphorescence properties of the resultant LRH materials. The lead formulation, LGd1.41Tb0.59H, was demonstrated to significantly shorten the T2 relaxation time of water (r2 = 52.06 mM-1 s-1), in addition to exhibiting a strong phosphorescence signal (over twice that of the other LRH formulations, including previously reported LTbH), therefore holding great promise as a potential multi-modal medical imaging probe.

Triplet-triplet energy transfer between host and guest induced strong phosphorescence in the organic doped system

Recently, purely organic room-temperature phosphorescence (RTP) from guest-host-doped systems has grown exponentially due to their high modulation flexibility. Benzophenone has been found as a preferred host matrix thanks to its low melting point, minimal biological toxicity, remarkable stability, and cost-effectiveness. However, the precise role of benzophenone remains elusive and has been debated within the scientific community concerning mechanistic elucidations. Here, five indole derivatives were designed and synthesized as guest molecules while retaining benzophenone as the host to construct doped materials exhibiting outstanding RTP properties. Our experimental findings unequivocally establish that the host benzophenone initially absorbs excitation energy, subsequently intersystem crossing into triplet exciton, facilitating the exciton transfer to guest molecule through the triplet energy transfer and culminating in guest RTP emission. Mechanistic investigation corroborates the superiority of benzophenone in possessing a large spin-orbit coupling constant and quantitatively triplet energy transfer. Collectively, this work provides compelling evidence deciphering energy transfer between host and guest entities for the manifestation of phosphorescence performance in benzophenone-hosted doped materials.

Sterically Hindered Tetradentate [Pt(O^N^C^N)] Emitters with Radiative Decay Rates up to 5.3 × 105 s-1 for Phosphorescent Organic Light-Emitting Diodes with LT95 Lifetime over 9200 h at 1000cd m-2.

Described here are sterically hindered tetradentate [Pt(O^N^C^N)] emitters (Pt-1, Pt-2, and Pt-3) developed for stable and high-performance green phosphorescent organic light-emitting diodes (OLEDs). These Pt(II) emitters exhibit strong saturated green phosphorescence (λmax = 517-531nm) in toluene and mCP thin films with emission quantum yields as high as 0.97, radiative rate constants (kr) as high as 4.4-5.3 × 105 s-1 and reduced excimer emission, and with a preferential horizontally oriented transition dipole ratio of up to 84%. Theoreticalcalculations show that p-(hetero)arene substituents at the periphery of the ligand scaffolds in Pt-1, Pt-2, and Pt-3 can i) enhance the spin-orbit coupling (SOC) between the lower singlet excited states and the T1 state, and S0→Sn (n = 1 or 2) transition dipole moment, and ii) introducing additional SOC activity and the bright 1ILCT[π(carbazole)→π*(N^C^N)] excited state (Pt-2 and Pt-3), which are the main contributors to the increased kr values. Utilizing these tetradentate Pt(II) emitters, green phosphorescent OLEDs are fabricated with narrow-band electroluminescence (FWHM down to 36nm), high external quantum efficiency, current efficiency up to 27.6% and 98.7cd A-1, and an unprecedented device lifetime (LT95) of up to 9270 h at 1000cd m-2 under laboratory conditions.

Cyclometalated Ir(III) Complexes as Lysosome-Targeted Photodynamic Anticancer Agents.

We have designed and synthesized two Ir(III) complexes (Ir1 and Ir2) coordinated with an 8-sulfonamidoquinoline derivative ligand as photosensitizers, which exhibit strong red phosphorescence emission and a long phosphorescence lifetime. The Ir(III) complexes exhibit a high population of triplet states, which enable red phosphorescence and efficient singlet oxygen generation. Ir1 and Ir2 rapidly enter the cancer cells and accumulate in lysosomes, producing large amounts of intracellular singlet oxygen when exposed to light irradiation, eventually leading to cancer cell death, and the phototoxic indexes of complexes Ir1 and Ir2 against cancer cells are in the range of 76-228. Overall, our studies indicate that the synthesized Ir(III) complexes with quinoline ligands exhibit photosensitizing properties, effectively inducing cancer cell death when exposed to light. These promising results suggest their potential application in photodynamic therapy.

Fabrication of Microcapsule-Type Long-Lasting Phosphorescent Sensor for Concrete Crack Monitoring

The generation and expansion of cracks in concrete structures reduce the durability and safety of structures. In order to detect cracks in concrete structures, a long-lasting phosphorescent microcapsule coating is proposed in this study. The microcapsule-based sensor is pasted on the surface of cement-based materials and solidified. The microcapsules become ruptured and cause the core material to flow out when the microcracks occur on the material, which emits strong phosphorescence at the cracked position under UV irradiation. The results indicate that the successful encapsulation of microcapsules could enhance the thermal stability of phosphorescent dye. The excitation wavelength of the phosphorescent microcapsules is also investigated. The phosphorescent microcapsules could effectively highlight unnoticeable cracks by a long-lasting phosphorescence response in the cracking region. The mechanical properties of microcapsules/epoxy resin composite coatings were studied, and the optimal content of microcapsules in the coating was determined. The as-fabricated phosphorescent microcapsules have good damage-sensing effects in conditions of different light and temperatures. The method proposed in this study will assist in the further development of damage-sensing material in the field of concrete crack monitoring.

Stimuli Responsive Features of Organic RTP Materials: An Intriguing Carbazole-Cyclic Triimidazole Derivative.

Stimuli responsive luminescent materials possessing room temperature phosphorescence (RTP) are extremely desirable for various applications. The here investigated derivative of cyclic triimidazole (TT) functionalized with carbazole (Cz), namely TT-Ph-Cz, belongs to this class. TT-Ph-Cz possesses high conformational freedom resulting in rigidochromic and multi-stimuli responsive emissive behavior. It has been isolated as MeOH-solvated and de-solvated forms characterized by distinctive emissive features. In particular, the solvated form, in which hydrogen bonds with MeOH inhibit competitive non-radiative deactivation channels, possesses a higher quantum yield associated with a strong phosphorescence contribution which is preserved in DMSO/water solutions.

Bis[1]benzothieno[1,4]thiaborins as a Platform for BODIPY Singlet Oxygen Photosensitizers.

A synthetic approach to two regioisomeric π-electron extended [1,4]thiaborins annulated with two benzothiophene units has been developed. The central thiaborin rings of the boracycles obtained exhibit different electronic properties; this is reflected in their different aromatic characters, boron Lewis acidity and UV-vis spectroscopic behavior. Thiaborins were converted to boron dipyrromethene (BODIPY) complexes. Their emission spectra exhibit two distinct bands resulting from 1 LE and 1 CT transitions. Strong near-infrared phosphorescence in Zeonex thin films at 77 K indicates efficient intersystem crossing and the formation of triplet states. Separation of HOMO and LUMO orbitals between boracyclic and BODIPY moieties facilitates electron transfer to a 1 CT state followed by a transition to the 3 LE triplet state located on the ligand. These unique properties of spiro thiaborin-BODIPY complexes were explored for their application as singlet-oxygen photosensitizers. They show excellent photocatalytic performance with singlet oxygen quantum yields reaching 77 % and full conversion of the model organic substrate achieved after 1.5 h with only 0.05 % mol catalyst load.

Hydrogen bonds and space restriction promoting long-lived room-temperature phosphorescence and its application for white light-emitting diodes

Achieving the long-lived and strong room-temperature phosphorescence (RTP) is challengeable but desirable, especially for the enhanced phosphorescence and metal-free nanomaterials. Herein, we initially synthesized the green-fluorescence carbon dots (pm-CDs), and further obtained the composite of pm-CDs@DCDA with a long RTP lifetime of 1.01 s through embedding pm-CDs in dicyandiamide (DCDA). And the bright and long-lived afterglow of pm-CDs@DCDA with 365 nm of UV light excitation was observed by the naked eyes for more than 17 s either emerging as the dry solid or in water. Importantly, the phosphorescence intensity and lifetime of pm-CDs@DCDA were remarkably promoted owing to the intermolecular hydrogen bonds and the rigid environment, hence facilitating the intersystem crossing (ISC) process and restricting the non-radiative transition of triplet excitons. Taking advantage of the superior solid-state luminescence of pm-CDs@DCDA, we further innovatively prepared the white light-emitting diodes (WLEDs) with the tunable color temperatures by regulating the mass of pm-CDs@DCDA coated on the chips. This proposed study originally employed DCDA as a matrix to separate and immobilize pm-CDs, which built up a new avenue to improve the RTP property and offered a promising application in WLEDs.

Turn on of room temperature phosphorescence of donor-acceptor-donor type compounds via transformation of excited states by rigid hosts for oxygen sensing

A series of compounds with the different donor moieties (phenothiazine, phenoxazine and acridine) and 1,4-difluorobenzene unit as the acceptor were developed for optical sensors of oxygen. Among three new compounds, oxygen sensing ability of one compound 10,10'-(2,5-difluoro-1,4-phenylene)bis(10 H-phenothiazine) (2PS-2FPh) exhibiting strong room-temperature phosphorescence in rigid matrix Zeonex shows high sensitivity to low concentration of oxygen (<0.1%). To understand the reason of the high oxygen sensitivity of 2PS-2FPh, the effect of a rigid medium on conformational distortion was studied using a set of experimental and theoretical approaches. Doping 2PS-2FPh into Zeonex results in strong room-temperature phosphorescence in a vacuum with singlet-triplet splitting (ΔEST) widened to 0.47 eV as compared to 0.17 eV observed for the solution in 2-methyltetrahydrofuran. Molecular dynamic simulation with 2PS-2FPh doped in Zeonex indicates the increased molecular heterogeneity. Concomitantly, the hybrid local and charge transfer triplet state (3HLCT) becomes more local allowing the room temperature phosphorescence to be observed from locally excited triplet states. These results showed that conformational disorder and rigidity of the medium can significantly widen ΔEST of donor-acceptor-donor type molecules transforming 3HLCT into 3LE and thus facilitating the room-temperature phosphorescence and high oxygen sensitivity of 2PS-2FPh.

Microfluidic-based modulation of triplet exciton decay in organic phosphorescent nanoparticles for size-assisted photodynamic antibacterial therapy.

The modulation of triplet exciton decay in organic room-temperature phosphorescence (RTP) materials has been considered as a promising strategy for highly efficient photodynamic therapy. In this study, we report an effective approach based on microfluidic technology to manipulate the triplet exciton decay for generating highly reactive oxygen species (ROS). BQD shows strong phosphorescence upon doping into crystalline BP, indicating the high generation of triplet excitons based on the host-guest interaction. Through microfluidic technology, BP/BQD doping materials can be precisely assembled to form uniform nanoparticles with no phosphorescence but strong ROS generation. The energy decay of the long-lived triplet excitons of BP/BQD nanoparticles emitting phosphorescence has been successfully manipulated via microfluidic technology to generate 20-fold enhanced ROS than that of BP/BQD nanoparticles prepared by nanoprecipitation. The in vitro antibacterial studies indicate that BP/BQD nanoparticles have high specificity against S. aureus microorganisms with a low minimum inhibition concentration (10-7 M). BP/BQD nanoparticles below 300 nm show size-assisted antibacterial activity, demonstrated using a newly developed biophysical model. This novel microfluidic platform provides an efficient approach to convert host-guest RTP materials into photodynamic antibacterial agents and to promote the development of antibacterial agents without cytotoxicity and drug-resistance issues based on the host-guest RTP systems.

Highly Emissive Luminogens in Both Solution and Aggregate States

Highly Emissive Luminogens in Both Solution and Aggregate States

Two‐Dimensional Perovskites with Tunable Room‐Temperature Phosphorescence

AbstractFunctional materials with room‐temperature phosphorescence (RTP) are highly desired for optoelectronic and bio‐imaging applications. Currently, most inorganic RTP materials require exceedingly expensive rare metals. Although organic materials have the advantages of low cost and facile fabrication, their quantum yields are quite poor due to low efficiency in the intersystem crossing process. 2D hybrid organic‐inorganic perovskites (2D HOIPs), however, entail the virtue of both inorganic and organic RTP materials, thereby capable of strong and persistent phosphorescence for making future‐generation RTP materials. Herein, an effective screening approach is presented to search for 2D HOIPs as efficient RTP materials. The guidelines for this high‐throughput screening include the Dexter‐type energy transfer mechanism, the computed excited‐state properties, and the molecular morphing operators. Moreover, the structural stability of the 2D HOIPs is assessed by using a newly proposed tolerance factor. Overall, 539 candidates are identified as promising 2D HOIP materials for RTP. In particular, four 2D HOIPs, namely, (thNfuEA)2PbBr4, (selBthEA)2PbBr4, (selBfuEA)2PbBr4, and (BselBthEA)2PbBr4, are predicted to possess robust room‐temperature stability, suitable energy level and proper frontier‐orbital alignment, thus hold high potential for functional optoelectronic applications.