Enhancement Of Room-temperature Phosphorescence Research Articles

Combining Functional Units to Design Organic Materials with Dynamic Room-Temperature Phosphorescence under Continuous Ultraviolet Irradiation.

Developing materials with dynamic room-temperature phosphorescence (RTP) properties is crucial for expanding the applications of organic light-emitting materials. In this study, we designed and synthesized two novel RTP molecules by combining functional units, incorporating the folded unit thianthrene into the classic luminescent cores thioxanthone or anthraquinone to construct TASO and TA2O. In this combination, the TA unit contributes to the enhancement of spin-orbit coupling (SOC), while the luminescent core governs the triplet energy level. After the strategic manipulation of SOC using the thianthrene unit, the target molecules exhibited a remarkable enhancement in RTP performance. This strategy led to the successful development of TASO and TA2O molecules with outstanding dynamic RTP properties when exposed to continuous ultraviolet irradiation, a result that can be ascribed to their efficient RTP, improved absorption ability, and oxygen-sensitive RTP properties. Leveraging the oxygen-mediated ultraviolet-radiation-induced RTP enhancement in TASO-doped polymer films, we developed a novel time-resolved detection technique for identifying phase separation in polymers with varying oxygen permeability. This research offers a promising approach for constructing materials with dynamic RTP properties.

Enhancing Purely Organic Room Temperature Phosphorescence via Supramolecular Self-Assembly.

Long-lived and highly efficient room temperature phosphorescence (RTP) materials are in high demand for practical applications in lighting and display, security signboards, and anti-counterfeiting. Achieving RTP in aqueous solutions, near-infrared (NIR) phosphorescence emission, and NIR-excited RTP are crucial for applications in bio-imaging, but these goals pose significant challenges. Supramolecular self-assembly provides an effective strategy to address the above problems. This review focuses on the recent advances in the enhancement of RTP via supramolecular self-assembly, covering four key aspects: small molecular self-assembly, cocrystals, the self-assembly of macrocyclic hosts and guests, and multi-stage supramolecular self-assembly. This review not only highlights progress in these areas but also underscores the prominent challenges associated with developing supramolecular RTP materials. The resulting strategies for the development of high-performance supramolecular RTP materials are discussed, aiming to satisfy the practical applications of RTP materials in biomedical science.

Host-guest interaction induced room-temperature phosphorescence enhancement of organic dyes: a computational study.

To achieve the effective regulation of organic room temperature phosphorescence (RTP) in supramolecular systems, the elucidation of host-guest interactions in RTP is of vital importance. Herein, we employed two organic dyes (PYCl and PYBr) and their four host-guest complexes with CB[6] and CB[7] and explored the mechanism of host-guest interaction induced RTP enhancement using quantum mechanics/molecular mechanics (QM/MM) approach. For the two organic dyes, we found that the better RTP performance of PYBr than PYCl is attributed to intersystem crossing (ISC) augmentation induced by the heavy atom effect. Binding to CB[6] through host-guest interactions can simultaneously accelerate the radiative decay process by increasing the transition dipole moment of T1 → S0 (μT1→S0), block the nonradiative decay process, and promote the ISC process, eventually leading to a remarkably boosted RTP. Upon complexation, the conversion of S1 from 1(n, π*) to 1(π, π*) is key to μT1→S0 enhancement; reduced reorganization energies reflect the suppression of the nonradiative decay process by restricting the rotation of rings A and B in organic dyes. In addition, the promoted ISC process is due to the activation of more ISC channels between S1 and high-lying triplet states with large spin-orbital coupling constants and small energy gap. The case of CB[7]-type complexes is much different, because of the extremely large cavity size of CB[7] for encapsulation. This work proposes the mechanism of host-guest interaction-induced RTP enhancement of organic dyes, thus laying a solid foundation for the rational design of advanced RTP materials based on supramolecular assemblies.

Photo-Responsive Dynamic Organic Room-Temperature Phosphorescence Materials Based on a Functional Unit Combination Strategy.

A rational molecular design strategy facilitates the development of a purely organic room-temperature phosphorescence (RTP) material system with precisely regulated luminescence properties, which surely promotes its functional integration and intelligent application. Here, a functional unit combination strategy is proposed to design novel RTP molecules combining a folding unit with diverse luminescent cores. The different luminescent cores are mainly responsible for tunable RTP properties, while the folding unit contributes to the spin-orbit coupling (SOC) enhancement, which makes the RTP material design as workable as the building block principle. By this strategy, a series of color/lifetime-tunable RTP materials is achieved with unique photo-responsive RTP enhancement when subjected to UV irradiation, which expands their application scenarios in reusable privacy tags, advanced "4D" encryption, and phase separation analysis of blended polymers. This work suggests a simple and effective strategy to design purely organic RTP materials with tunable color and lifetime, and also provides new application options for photo-responsive dynamic RTP materials.

Aqueous Solution Enhanced Room Temperature Phosphorescence through Coordination-Induced Structural Rigidity.

Achieving aqueous solution enhanced room temperature phosphorescence (RTP) is critical for the applications of RTP materials in solution phase, but which faces a great challenge. Herein, for the first time, a strategy of coordination-induced structural rigidity is proposed to achieve enhanced quantum efficiency of aluminum/scandium-doped phosphorescent microcubes (Al/Sc-PMCs) in aqueous solution. The Al/Sc-PMCs in a dry state exhibit a nearly invisible blue RTP. However, they emit a strong RTP emission in aqueous solution with a RTP intensity increase of up to 22.16-times, which is opposite to common solution-quenched RTP. The RTP enhancement mechanism is attributed to the abundant metal sites (Al3+ and Sc3+ ions) on the Al/Sc-PMCs surface that can tightly combine with water molecules through the strong coordination. Subsequently, these coordinated water molecules as the bridging agent can bind with surface groups by hydrogen bonding interaction, thereby rigidifying chemical groups and inhibiting their motions, resulting in the transition from the nonradiative decay to the radiative decay, which greatly enhances the RTP efficiency of the Al/Sc-PMCs. This work not only develops a coordination rigidity strategy to enhance RTP intensity in aqueous solution, but also constructs a phosphorescent probe to achieve reliable and accurate determination of analyte in complex biological matrices.

Observation of Chiral-selective room-temperature phosphorescence enhancement via chirality-dependent energy transfer

Pure organic room-temperature phosphorescence (RTP), particularly from guest-host doped systems, has seen exponential growth in the last several years due to their high modulation flexibility, and yet challenges remain with respect to mechanistic elucidations and advantageous applications. Here we show that by constructing guest-host doped RTP systems from chiral components, namely, chiral amino compound-modified phthalimide hosts and naphthalimide guests, a chiral-selective RTP enhancement phenomenon can be observed. For example, R-enantiomeric guests in R-enantiomeric hosts produce strong red RTP afterglow while no appreciable RTP could be observed in the S-R guest-host counterpart. An unprecedented RTP intensity difference > 102 folds with the ability to distinguish an enantiomeric excess of 98% could be achieved. Temperature-dependent measurements suggest that a chirality-dependent energy transfer process may be involved in the observed phenomenon, which can be harnessed to extend the RTP application to the chiral recognition of amino compounds, such as amino alcohols.

Role of Carbonyl Distortions Facilitating Persistent Room-Temperature Phosphorescence

A decrease in the room-temperature phosphorescence (RTP) yield and RTP lifetime with increasing temperature is often explained by the increased nonradiative transition from the lowest triplet excited state (T1) caused by molecular vibrations of the chromophores. Here, we report a positive contribution of molecular vibrations and the distortion of vanillic acid (VA) dispersed in amorphous insulating polymer hosts to phosphorescence characteristics. We investigated triplet generation as well as photophysical processes from T1 of VA dispersed in poly(methyl methacrylate) (PMMA) and poly(vinyl alcohol) (PVA). Comparisons between optically measured data and calculation-based data, regarding the phosphoresce rate (kp) and the rate constant of the nonradiative transition (knr) from T1, reveal that kp and knr of the dispersed VA negligibly changed in PMMA or PVA, indicating that intermolecular processes between VA and PMMA are related to a large RTP quenching of VA in PMMA. Vibrational out-of-plane distortion of the carbonyl moiety of VA induced ππ*–nπ* mixing between the high-order singlet excited state and the ground state, mainly enhancing kp compared with knr of VA. Although vibrations are often reported to quench RTP, this report suggests that some distortions induced by vibrations of other chromophores contribute to RTP enhancement of molecular solid materials.

Pressure-induced room-temperature phosphorescence enhancement based on purely organic molecules with a folded geometry.

The pressure-dependent luminescence behavior of purely organic compounds is an important topic in the field of stimulus-responsive smart materials. However, the relevant studies are mainly limited to the investigation of fluorescence properties, while room-temperature phosphorescence (RTP) of purely organic compounds has not been investigated. Here, we filled in this gap regarding pressure-dependent RTP by using a model molecule selenanthrene (SeAN) with a folded geometry. For the first time to the best of our knowledge, a unique phenomenon involving pressure-induced RTP enhancement was discovered in an SeAN crystal, and an underlying mechanism involving folding-induced spin-orbit coupling enhancement was revealed. Pressure-induced RTP enhancement was also observed in an analog of SeAN also showing a folded geometry, but in this case yielded a white-light emission that is very rare in purely organic RTP-displaying materials.

Controllable Modulation of Efficient Phosphorescence Through Dynamic Metal‐Ligand Coordination for Reversible Anti‐Counterfeiting Printing of Thermal Development

AbstractDynamically tunable room‐temperature phosphorescence (RTP) organic materials have attracted considerable attention in recent years due to their great potential over a wide variety of advanced applications. However, the precise regulation of the intersystem crossing (ISC) process for efficient RTP materials with dynamically modulated properties in a rigid environment is challenging. Herein, an effective strategy for RTP material preparation with controllably regulated properties is developed via the construction of dynamic metal‐ligand coordination in a host‐guest doped system. The coordination interaction promotes ISC and phosphorescence emission of the guest, thus allowing the modulation of the photophysical properties of doped materials by changing the doping ratio and Zn2+ counterions. By taking advantage of the reversible metal‐ligand coordination interaction, the coordination‐activated, and dissociation‐deactivated RTP is dynamically manipulated. With the unique Zn2+‐responsible RTP enhancement materials, the anti‐counterfeiting applications of thermal development, and color inversion have been constructed for inkjet printing of high‐resolution patterns with high reversibility for many write/erase cycles. The results show that dynamic metal‐ligand coordination strategy is a promising approach for achieving efficient RTP materials with controllably modulated properties.

Very sensitive probes for quantitative and organoleptic detection of oxygen based on conformer-induced room-temperature phosphorescence enhancement of the derivative of triazatruxene and phenothiazine

Organic materials which show room-temperature phosphorescence (RTP) are of interest for many applications including chemical qubits which are the core units of a quantum information systems, organic light emitting diodes, chemical sensors. In contrast to triplet emitters based on noble metals (e.g. Ir, Rh), quantum yields of RTP of noble-atom-free organic emitters are much lower than unity. In this work, we report on a new approach to conformer-induced RTP enhancement of organic triplet emitters. The synthesis, thermal, photophysical, charge-transporting and oxygen sensing properties of the derivative of phenothiazine and triazatriazatruxene in which phenothiazine moieties are linked to nitrogen atoms of triazatriazatruxene via C-2 positions are presented. This compound exhibit stable RTP with a quantum yield of 54% which is more than six times higher than that of a reference material. For 1% solid solution of the compound in Zeonex, the ratio of intensity of RTP observed under vacuum and fluorescence intensity recorded in air reached the value of 19 which allows quantitative detection of oxygen with the high Stern-Volmer quenching constant of 7.83 × 10−3 ppm−1. The observed change of emission colour depending on the oxygen concentration can be used for the simple detection of oxygen by human eye.

Color‐tunable room temperature phosphorescence mediated by host–guest chemistry and stimuli‐responsive polymer matrices

AbstractColor‐tunable room temperature phosphorescence (RTP) luminescent materials with stimuli‐responsive properties are highly desirable for practical applications, but the fundamental design principles still need further exploitation. Herein, we report on the extended red‐shifted multicolor RTP afterglow from blue to orange, including white light, offered by a series of newly designed supramolecular polymers based on 1‐([2‐methylallyl]oxy)pyrene phosphor‐containing guest polymers and β‐cyclodextrin (β‐CD)/γ‐CD host molecules. RTP enhancement is efficiently realized, attributing to the strong restriction on the dimeric pyrene units by the host–guest inclusion complexation of CDs and the multiple interactions amongst polymer matrices and phosphorescent moieties. Interestingly, a more comprehensive blue‐shifted color tuning range is also enabled upon introducing pH‐sensitive fragments due to the self‐assembly of the ternary polymers aided by ionic bonding. Notably, optimized intelligent multicolor RTP systems induced by altered external stimuli, including concentration, irradiation, and pH, are established, showing great potential in developing stimuli‐responsive luminescent materials for practical applications. In addition, theoretical calculations are conducted to elucidate diverse emission mechanisms of pyrene units in different assembly states.

Structurally Resemblant Dopants Enhance Organic Room-Temperature Phosphorescence.

Doping has shown very promising potential in endowing room-temperature phosphorescence (RTP) properties of organic phosphors with minimal effort. Here, a new isomer design and doping strategy is reported that is applicable to dibenzothiophene (DBT) and its derivatives. Three isomers are synthesized to study the dopant effect on enhancing RTP of DBT derivatives. It is found that isomer dopants bearing close resemblance to the host with matched highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels and small energy difference between singlet- and triplet-excited states can yield efficient RTP for the doped system. Meanwhile, phosphorescence color from yellow to red is achieved by varying isomer dopants used for doping the DBT derivatives. This work represents an RTP enhancement strategy based on isomer design and doping to construct luminescent organic phosphors.

Mesoporous silica-deoxycholate synergistic substrate, a novel room temperature phosphorescence-sensing platform

A novel mesoporous silica-deoxycholate (MS-NaDC) synergistic substrate was developed for room-temperature phosphorescence (RTP) sensing and analysis. The substrate exhibited rapid and strong RTP-inducing ability toward 9-bromophenanthrene (9-BrP). The formation mechanism of MS-NaDC synergistic substrate was analyzed and demonstrated. Five MSs with pore size range of 2.73–18.58nm were synthesized and investigated, and the MS designated as LPMS2 was selected for its rapid RTP protection and good stability in dispersions. RTP in the presence of MS-NaDC substrate also shows good thermostability. Assistant inducers, such as cyclohexane, can be used together for further RTP enhancement. Finally, 9-BrP holds a fairly wide linear concentration range of 2nM–3μM, and a detection limit of 0.5nM. All the results demonstrated the feasibility and application potential of the MS-NaDC substrate in RTP.

ChemInform Abstract: Room‐Temperature Phosphorescence from Purely Organic Materials

AbstractReview: [41 refs.

Room-temperature phosphorescence from purely organic materials

Abstract Room-temperature phosphorescence (RTP) materials have attracted great attention due to their involvement of excited triplet states and comparatively long decay lifetimes. In this short review, recent progress on enhancement of RTP from purely organic materials is summarized. According to the mechanism of phosphorescence emission, two principles are discussed to construct efficient RTP materials: one is promoting intersystem crossing (ISC) efficiency by using aromatic carbonyl, heavy-atom, or/and heterocycle/heteroatom containing compounds; the other is suppressing intramolecular motion and intermolecular collision which can quench excited triplet states, including embedding phosphors into polymers and packing them tightly in crystals. With aforementioned strategies, RTP from purely organic materials was achieved both in fluid and rigid media.

Mn-Doped ZnS Quantum Dot Imbedded Two-Fragment Imprinting Silica for Enhanced Room Temperature Phosphorescence Probing of Domoic Acid

A novel strategy was presented to construct the enhanced molecularly imprinted polymer (MIP)-based room temperature phosphorescence (RTP) probe by combining the RTP of Mn-doped ZnS quantum dots (Mn-ZnS QDs) and two-fragment imprinting. Two fragments or structurally similar parts of the target analytes were used as the dummy templates. Polyethyleneimine capped Mn-ZnS (PEI-Mn-ZnS) QDs, offering the binding sites to interact with the carboxyl groups of templates, were imbedded into MIPs by the hydrolysis of tetraethoxysilane. The rebinding of the target analytes to their fragments' cavities (recognition sites) modulated the selective aggregation of Mn-ZnS QDs in QDs-MIPs and resulted in the RTP enhancement. This new method was suitable for the selective enhanced RTP detection of nonphosphorescent analytes without any derivatization and inducers. The proposed methodology was applied to construct the high selective enhanced MIP-based RTP probe for domoic acid (DA) detection. The RTP enhancement of two-fragment imprinting silica was about 2 times of one-fragment imprinting silica and 4 times of the nonimprinting silica. The two-fragment imprinting silica exhibited the linear RTP enhancement to DA in the range of 0.25-3.5 μM in buffer and 0.25-1.5 μM in shellfish sample. The precision for 11 replicate detections of 1.25 μM DA was 0.65% (RSD), and the limit of detection was 67 nM in buffer and 2.0 μg g(-1) wet weight (w/w) in shellfish sample.

Ascorbic Acid Induced Enhancement of Room Temperature Phosphorescence of Sodium Tripolyphosphate‐Capped Mn‐Doped ZnS Quantum Dots: Mechanism and Bioprobe Applications

Although quantum dot (QD)-based room temperature phosphorescence (RTP) probes are promising for practical applications in complex matrixes such as environmental, food and biological samples, current QD-based-RTP probes are not only quite limited but also exclusively based on the RTP quenching mechanism. Here we report an ascorbic acid (AA) induced phosphorescence enhancement of sodium tripolyphosphate-capped Mn-doped ZnS QDs, and its application for turn-on RTP detection. The chelating ability allows AA to extract the Mn and Zn from the surface of the QDs and to generate more holes which are subsequently trapped by Mn(2+), while the reducing property permits AA to reduce Mn(3+) to Mn(2+) in the excited state, thereby enhancing the excitation and orange emission of the QDs. The enhanced RTP intensity of the QDs increases linearly with the concentration of AA in the range of 0.05-0.8 μM. Thus, a QD-based RTP probe for AA is developed. The proposed QD-based turn-on RTP probe avoids tedious sample pretreatment, and offers good sensitivity and selectivity for AA in the presence of the main relevant metal ions and other molecules in biological fluids. The limit of detection (3s) of the developed method is 9 nM AA, and the relative standard deviation is 4.8 % for 11 replicate detections of 0.1 μM AA. The developed method is successfully applied to the analysis of real samples of human urine and plasma for AA with quantitative recoveries from 96 to 105 %.

Room temperature phosphorescence of 6-bromo-2-naphthol in micelles of poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) block copolymers and in their mixed aggregates with sodium dodecyl sulfate

Room temperature phosphorescence (RTP) of 6-bromo-2-naphthol has been investigated in aqueous micellar solutions of poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) block copolymers as well as in their mixed aggregates with sodium dodecyl sulfate. RTP of the phosphorophor was enhanced to some extent in the micelles of the block copolymers. However, marked enhancement of RTP was observed in the mixed aggregates. The enhancement of RTP is attributed to effective incorporation of the phosphorophor into the micelles and the aggregates, resulting in suppression of nonradiative deactivation of the phosphorescent state.

Cyclodextrin-induced fluid solution room-temperature phosphorescence from acenaphthene in the presence of 2-bromoethanol

A 1:1 stoichiometric ratio and a formation constant of 130 1 mol −1 were obtained for the binary inclusion complex between acenaphthene and β-cyclodextrin (CD). On addition of 2-bromoethanol, effective quenching of the fluorescence emission and enhancement of the room-temperature phosphorescence (RTP) of acenaphthene is observed. The use of 2-bromoethanol as an external “heavy atom” to obtain room-temperature phosphorescence in fluid solutions is discussed. The RTP emission from acenaphthene included in β-CD was optimized and characterized. The apparent formation constant of the ternary associate was determined to be 880 1 mol −1 by the use of RTP enhancement in the presence of 1% 2-bromoethanol. The data indicate a ternary association between acenaphthene, β-CD and the bromo alcohol. The use of sodium sulfite, for chemical deoxygenation, to obtain RTP emission from a non-heavy atom-containing luminophor is shown to be feasible. The kinetics of the deoxygenation reaction were established and a photochemical catalytic effect on the reaction was demonstrated.

Studies of cyclodextrin-enhanced room-temperature phosphorescence

The enhancement of room-temperature phosphorescence by α-, β- and γ-cyclodextrins in the presence of heavy atoms is described for p-aminobenzoic acid, anthracene and six of its derivatives, dibenzofuran and some other compounds. The sensitivity can be improved by treating the filter paper substrate with the cyclodextrin (preferably β-cyclodextrin) or by mixing the analyte with β-cyclodextrin prior to sample spotting on the substrate.