Room Temperature Phosphorescence Research Articles

Supermolecular Confined Silicon Phosphorescence Nanoprobes for Time-Resolved Hypoxic Imaging Analysis.

Room temperature phosphorescence (RTP) nanoprobes play crucial roles in hypoxia imaging due to their high signal-to-background ratio (SBR) in the time domain. However, synthesizing RTP probes in aqueous media with a small size and high quantum yield remains challenging for intracellular hypoxic imaging up to present. Herein, aqueous RTP nanoprobes consisting of naphthalene anhydride derivatives, cucurbit[7]uril (CB[7]), and organosilicon are reported via supermolecular confined methods. Benefiting from the noncovalent confinement of CB[7] and hydrolysis reactions of organosilicon, such small-sized RTP nanoprobes (5-10 nm) exhibit inherent tunable phosphorescence (from 400 to 680 nm) with microsecond second lifetimes (up to ∼158.7 μs) and high quantum yield (up to ∼30%). The as-prepared RTP nanoprobes illustrate excellent intracellular hypoxia responsibility in a broad range from ∼0.1 to 21% oxygen concentrations. Compared to traditional fluorescence mode, the SBR value (∼108.69) of microsecond-range time-resolved in vitro imaging is up to 2.26 times greater in severe hypoxia (<0.1% O2), offering opportunities for precision imaging analysis in a hypoxic environment.

Cationic Engineering Strategy to Achieve Controllable Room‐Temperature‐Phosphorescence in Hybrid Zinc Halides

AbstractDespite rapid progress and wide applications of room temperature phosphorescence (RTP) materials, it is still a great challenge to optimize the RTP activity through rational structural design at a molecular level. Herein, a successful cationic engineering strategy is demonstrated to modulate the crystal flexibility achieving controllable RTP in a new pair of metal halides [APML]ZnCl4 ([APML] = N‐(3‐Aminopropyl)morpholine) and [AEML]ZnCl4 ([AEML] = N‐(2‐Aminoethyl)morpholine). Both halides display blue fluorescence under 365 nm UV. Comparing with longer [APML]+, shorter [AEML]+ significantly enhances crystal rigidity and restrains non‐radiative scattering, boosting photoluminescence quantum yield (PLQY) from 18.89% to 22.41%. Synchronously, enhanced crystal rigidity significantly promotes the inter‐system crossing from singlet to triplet excited states. As a consequence, [AEML]ZnCl4 displays long‐lived green RTP property with millisecond scale lifetime in contrast to the blank RTP activity of [APML]ZnCl4. Comprehensive investigations demonstrate that the energy transfer between inorganic and organic components greatly changes the redistribution of singlet and triplet excited states, resulting in distinct phosphorescence activity. The different short‐lived blue fluorescence and long‐lived green phosphorescence provide a color‐time‐dual‐resolved luminescent tag with advanced applications in anti‐counterfeiting, etc. This work highlights a new structural engineering strategy to achieve controllable RTP affording a guide to rationally design RTP materials.

Controllable Blue Shift and Enhancement Emission during the Gradually Increasing Molecular Weight of Polyacrylamide.

Nonconventional luminescent polymers have become research hotspots due to their advantages such as persistent room temperature phosphorescence (p-RTP) emission and strong film-forming properties. It has been proven that the molecular weight(MW) of such luminescent polymers has a significant impact on their emission over a large range, generally with a red shift as the MW increases. Herein, four controllable MW polyacrylamide (PAM) were prepared via Reversible addition-fragmentation chain transfer polymerization (RAFT) polymerization, and their photoluminescence quantum yield (PLQY) and p-RTP lifetimes gradually increase with the increasing MW. The emission of p-RTP gradually shifts blue with increasing MW, which is likely due to the gradually changing interactions between the electron rich portion in RAFT reagent and the increasing AM units in the molecular chain. These can be reasonably explained through small angle X-ray scattering (SAXS), the clustering triggered emission (CTE) mechanism and supported by theoretical calculations. Powder with controllable p-RTP capability has the potential for strategic anti-counterfeiting encryption. The above results not only promote the development of CTE mechanism towards more precise explanations, but also provide new ideas for the preparation of nonconventional luminescent polymers with controllable p-RTP emission performance. This article is protected by copyright. All rights reserved.

Long lifetimes white afterglow in slightly crosslinked polymer systems

Intrinsic polymer room-temperature phosphorescence (IPRTP) materials have attracted considerable attention for application in flexible electronics, information encryption, lighting displays, and other fields due to their excellent processabilities and luminescence properties. However, achieving multicolor long-lived luminescence, particularly white afterglow, in undoped polymers is challenging. Herein, we propose a strategy of covalently coupling different conjugated chromophores with poly(acrylic acid (AA)-AA-N-succinimide ester) (PAA-NHS) by a simple and rapid one-pot reaction to obtain pure polymers with long-lived RTPs of various colors. Among these polymers, the highest phosphorescence quantum yield of PAPHE reaches 14.7%. Furthermore, the afterglow colors of polymers can be modulated from blue to red by introducing three chromophores into them. Importantly, the acquired polymer TPAP-514 exhibits a white afterglow at room temperature with the chromaticity coordinates (0.33, 0.33) when the ratio of chromophores reaches a suitable value owing to the three-primary-color mechanism. Systematic studies prove that the emission comes from the superposition of different triplet excited states of the three components. Moreover, the potential applications of the obtained polymers in light-emitting diodes and dynamic anti-counterfeiting are explored. The proposed strategy provides a new idea for constructing intrinsic polymers with diverse white-light emission RTPs.

Room‐Temperature Phosphorescence Hydrogel with Multiple Color Based on Salt‐Induced Aggregation

AbstractOrganic photoluminescent materials with room‐temperature phosphorescence (RTP) are of great interest, yet achieving RTP in hydrogels faces challenges due to water‐quenching effects. In this study, a straightforward method is presented to achieve RTP hydrogel using a self‐healing and salt‐hardening hydrogel. The hydrogel is synthesized by polymerizing acrylic acid (AA) with diethylenetriamine (DETA) as the dynamic crosslinker. The poly(acrylic acid)/DETA hydrogel could achieve an afterglow lasting 1.6 s after soaking with NaBr solution. The salt‐enhanced hydrophobic aggregation of the hydrogel network promotes the clustering of carboxyl groups and oxygen atoms, resulting in a rigid environment that suppresses nonradioactive transitions and leads to the manifestation of RTP. Additionally, the dynamic association of AA‐DETA allows the freeze‐dried hydrogel powder to be blended with various hydrophobic dyes, leading to a remodelable hydrogel with delayed emission of multiple colors. In general, by combining salt‐hardening property with self‐healing property together, a RTP hydrogel platform that can be facilely loaded with various organic dyes is proposed.

Solid‐State Photochemical Cascade Process Boosting Smart Ultralong Room‐Temperature Phosphorescence in Bismuth Halides

AbstractMolecular ultralong room‐temperature phosphorescence (RTP), exhibiting multiple stimuli‐responsive characteristics, has garnered considerable attention due to its potential applications in light‐emitting devices, sensors, and information safety. This work proposes the utilization of photochemical cascade processes (PCCPs) in molecular crystals to design a stepwise smart RTP switch. By harnessing the sequential dynamics of photo‐burst movement (induced by [2+2] photocycloaddition) and photochromism (induced by photogenerated radicals) in a bismuth (Bi)‐based metal‐organic halide (MOH), a continuous and photo‐responsive ultralong RTP can be achieved. Furthermore, utilizing the same Bi‐based MOH, diverse application demonstrations, such as multi‐mode anti‐counterfeiting and information encryption, can be easily implemented. This work thus not only serves as a proof‐of‐concept for the development of solid‐state PCCPs that integrate photosalient effect and photochromism with light‐chemical‐mechanical energy conversion, but also lays the groundwork for designing new Bi‐based MOHs with dynamically responsive ultralong RTP.

Solid-State Photochemical Cascade Process Boosting Smart Ultralong Room-Temperature Phosphorescence in Bismuth Halides.

Molecular ultralong room-temperature phosphorescence (RTP), exhibiting multiple stimuli-responsive characteristics, has garnered considerable attention due to its potential applications in light-emitting devices, sensors, and information safety. This work proposes the utilization of photochemical cascade processes (PCCPs) in molecular crystals to design a stepwise smart RTP switch. By harnessing the sequential dynamics of photo-burst movement (induced by [2+2] photocycloaddition) and photochromism (induced by photogenerated radicals) in a bismuth (Bi)-based metal-organic halide (MOH), a continuous and photo-responsive ultralong RTP can be achieved. Furthermore, utilizing the same Bi-based MOH, diverse application demonstrations, such as multi-mode anti-counterfeiting and information encryption, can be easily implemented. This work thus not only serves as a proof-of-concept for the development of solid-state PCCPs that integrate photosalient effect and photochromism with light-chemical-mechanical energy conversion, but also lays the groundwork for designing new Bi-based MOHs with dynamically responsive ultralong RTP.

Confinement of Sustainable Carbon Dots Results in Long Afterglow Emitters and Photocatalyst for Radical Photopolymerization.

Sustainable carbon dots based on cellulose, particularly carboxymethyl cellulose (CMCCDs), were confined in an inorganic network resulting in CMCCDs@SiO2. This resulted in a material exhibiting long afterglow covering a time frame of several seconds also under air. Temperature-dependent emission spectra gave information on temperature-assisted delayed fluorescence (TADF) and room temperature phosphorescence (RTP) while photocurrent experiments provided a deeper understanding of charge availability in the dark period, and therefore, its availability on the photocatalyst surface. The photo-ATRP initiator, ethyl(bromo)phenyl acetate (EBPA), quenched the emission from the millisecond to the nanosecond time frame indicating participation of the triplet state in photoinduced electron transfer (PET). Both free radical and living radical polymerization based on photo-ATRP protocol worked successfully. Metal-free photo-ATRP resulted in chain extendable macroinitiators based on a reductive mechanism with either MMA or in combination with styrene. Addition of 9 ppm Cu2+ resulted in Mw/Mn of 1.4 while an increase to 72 ppm improved uniformity of the polymers; that is Mw/Mn=1.03. Complementary experiments with kerria laca confined materials, namely KCDs@SiO2, provided similar results. Deposition of Cu2+ (9 ppm) on the photocatalyst surface explains better uniformity of the polymers formed in the ATRP protocol.

Confinement of Sustainable Carbon Dots Results in Long Afterglow Emitters and Photocatalyst for Radical Photopolymerization

Sustainable carbon dots based on cellulose, particularly carboxymethyl cellulose (CMCCDs), were confined in an inorganic network resulting in CMCCDs@SiO2. This resulted in a material exhibiting long afterglow covering a time frame of several seconds also under air. Temperature‐dependent emission spectra gave information on temperature‐assisted delayed fluorescence (TADF) and room temperature phosphorescence (RTP) while photocurrent experiments provided a deeper understanding of charge availability in the dark period, and therefore, its availability on the photocatalyst surface. The photo‐ATRP initiator, ethyl(bromo)phenyl acetate (EBPA), quenched the emission from the millisecond to the nanosecond time frame indicating participation of the triplet state in photoinduced electron transfer (PET). Both free radical and living radical polymerization based on photo‐ATRP protocol worked successfully. Metal‐free photo‐ATRP resulted in chain extendable macroinitiators based on a reductive mechanism with either MMA or in combination with styrene. Addition of 9 ppm Cu2+ resulted in Mw/Mn of 1.4 while an increase to 72 ppm improved uniformity of the polymers; that is Mw/Mn=1.03. Complementary experiments with kerria laca confined materials, namely KCDs@SiO2, provided similar results. Deposition of Cu2+ (9 ppm) on the photocatalyst surface explains better uniformity of the polymers formed in the ATRP protocol.

Carbon dot-based afterglow composite with tunable room temperature phosphorescence and thermally activated delayed fluorescence and their anti-counterfeiting and encryption application

Carbon dots (CDs) based afterglow materials have attracted much attention owing to their low toxicity, environmental protection, stable luminescence, abundant raw materials, and low cost. However, CD-based afterglow materials with both room temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) characteristics are rarely reported, which greatly limits their in-depth application in advanced anti-counterfeiting, intelligent sensing, and other fields. In this paper, Cu, N co-doped CDs (Cu, N-CDs) with dual emission centers were synthesized via a simple solvothermal method by heteroatom doping to enhance the spin–orbit coupling of CDs and regulate the luminescence properties of CDs. Then, boric acid (BA) was used as the matrix to synthesize Cu, N-CDs@BA composites by matrix-assisted method, and the electron transfer enhancement afterglow was realized by the inorganic electronic defects of the matrix. Cu, N-CDs@BA can realize the mutual conversion of TADF and RTP by changing the excitation wavelength or increasing the temperature. At the excitation of 285 nm, the room temperature afterglow of Cu, N-CDs@BA exhibit TADF, and the average afterglow lifetime is 94.21 ms. At the excitation of 365 nm, they exhibit RTP, and the average afterglow lifetime is 347.96 ms. Based on three different emission properties (fluorescence, RTP, and TADF), Cu, N-CDs@BA was applied in anti-counterfeiting and encryption, which shows good application potential.

Host-guest doped room/high-temperature phosphorescence of diarylfuro[3,2-b]pyridine derivatives

Due to the high temperature that can easily lead to non-radiative transitions of triplet excitons, obtaining high-temperature phosphorescence (HTP) materials is challenging. Herein, using diarylfuro[3,2-b]pyridines as the guest molecules and polyacrylic acid (PAA) as the host molecule, the two-component doped materials exhibit green room-temperature phosphorescence (RTP) with afterglow times of 2–8 s, delayed lifetimes of 256–939 ms, and phosphorescence quantum efficiencies of 140.3–21.2 %, and green HTP emissions with 2 s afterglow and 208 ms delayed lifetime at 373 K. The HTP activity of the doped system originates from the rigid environment provided by PAA, planar and rigid molecular structures of diarylfuro[3,2-b]pyridines, and strong interactions between PAA and diarylfuro[3,2-b]pyridines. Furthermore, using organic small molecules as the reference host molecules, compared to benzophenone, 5-methylphthalic anhydride, and butane-1,2,3,4-tetracarboxylic acid with chemical structures similar to PAA result in better RTP/HTP properties, revealing that strong interactions between host and guest molecules play a very important role in ultralong phosphorescence emissions of these host–guest doped materials. Moreover, these doped materials based on diarylfuro[3,2-b]pyridines can be developed as advanced anti-counterfeiting and encryption materials. This result provides valuable reference for developing excellent RTP/HTP materials based on N,O-containing fused-ring compounds.

Multiemitting Ultralong Phosphorescent Carbonized Polymer Dots via Synergistic Enhancement Structure Design.

Advancing a metal-free room temperature phosphorescent (RTP) material that exhibits multicolor emission, remarkable RTP lifetime, and high quantum yield still faces the challenge of achieving intersystem crossing between singly and triplet excited states, as well as the rapid decay of triplet excited states due to nonradiative losses. In this study, a novel strategy is proposed to address these limitations by incorporating o-phenylenediamine, which generates multiple luminescent centers, and long-chain polyacrylic acid to synthesize carbonized polymer dots (CPDs). These CPDs are then embedded in a rigid B2O3 matrix, effectively limiting nonradiative losses through the synergistic effects of polymer cross-linking and the rigid matrix. The resulting CPD-based materials exhibit remarkable ultralong phosphorescence in shades of blue and lime green, with a visible lifetime of up to 49 s and a high phosphorescence quantum yield. Simultaneously, this study demonstrates the practical applicability of these excellent material properties in anti-counterfeiting and information encryption.

Host-Guest Doping Modulated Afterglow Emission of Fluoroquinolones for Their Separation-Free Detection and Discrimination.

Detection and discrimination of fluoroquinolones (FQs) are crucial for food safety but remain a formidable challenge due to their minor differences in molecular structures and the serious interferences from food matrices. Herein, we propose an afterglow assay for the detection and discrimination of FQs through modulating their room-temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) properties by a host-guest doping strategy. FQs were doped into the boric acid host, forming boronic anhydride structures and hydrogen bonds, which prompted the RTP and TADF performance of FQs by stabilizing their excited states, preventing triplet exciton quenching, and reducing the energy gap between singlet and triplet states. The FQs can be quantitatively detected through monitoring the afterglow intensity of host-guest systems, as low as 0.25 μg/mL. The differences in the afterglow intensity and emission lifetime allowed accurate discrimination of 11 types of FQs through pattern recognition methods. Aided by the delayed signal detection model of afterglow emission, the background signal and the interferences from food matrices were effectively eliminated, which endow the detection and discrimination of mixed FQs in commercial meat samples, without multiple-step separation processes.

Ultralong MRTADF and Room‐Temperature Phosphorescence Enabled Color‐Tunable and High‐Temperature Dual‐Mode Organic Afterglow from Indolo[3,2‐b]carbazole

AbstractOrganic afterglow can be generated from persistent thermally activated delayed fluorescence (pTADF) or organic ultralong room temperature phosphorescence (OURTP), but the pTADF plus OURTP type organic afterglow is challenging to achieve, especially for the color‐tunable and high‐temperature ones. Herein, an accessible strategy toward such dual‐mode afterglow is presented by doping the indolo[3,2‐b]carbazole (ICZ‐p1) into polymethyl methacrylate (PMMA). The resulting films exhibit photo‐activated afterglow with two persistent emission peaks of ca. 435 and 497 nm. Impressively, their longest lifetimes respectively reach to 2.28 and 2.47 s at 298 K, along with 0.32 and 0.42 s at 360 K, enabling the afterglow at room and high temperature. Experimental and theoretical results reveal that the photo‐activated afterglow is associated with the elimination of molecular O2 inside film and composed by the pTADF with multi‐resonance (MR) effect and OURTP. By altering the temperature from 77 to 358 K, the color‐tunable afterglows of green and blue are harvested at such temperature ranges. Benefiting from the multi‐resonance thermally activated delayed fluorescence (MRTADF) characteristics, this emitter can release narrow‐band electroluminescence. Consequently, the results obtained here may offer important references for chasing MRTADF plus OURTP‐type dual‐mode organic afterglow showing color‐tunable and high‐temperature features.

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.

Fluorescence response of metalo-hydrogen-bonded organic framework (MHOF) with room temperature phosphorescence to organic pollutants

For health, environmental and safety reasons, it is necessary to conduct highly sensitive detection of organic contaminant antibiotics (sulfathiazole) and nitro explosive drugs (o-nitroaniline) in water. In this work, metal-hydrogen bonded organic framework (MHOF), {[Co(Ad)2(H2O)4]·(H2L)·2.5H2O}n (1), was synthesized by a one-pot hydrothermal method with 2,6-bis(3,5-dicarboxyphenoxy) pyridine (H4L) and adenine (Ad). This MHOF shows a 4-fold interpenetrated three-dimensional (3D) network structure. Importantly, 1 has excellent fluorescence properties and can be used as fluorescent chemical sensor to detect sulfathiazole (STZ) and 2-nitroanilin (2-NA) with limit of detection (LOD) 203 ppb and 6.8 ppb, respectively. By UV-vis absorption/emission spectroscopic measurements and DFT calculations, it is found that photoinduced electron transfer (PET) and fluorescence resonance energy transfer (FRET) are two potential quenching processes. This is the first report of metal-hydrogen bond organic frameworks (MHOFs) as a promising new fluorescent chemical sensor for the detection of organic pollutants in water.

Multi-Functional Integration of Phosphor, Initiator, and Crosslinker for the Photo-Polymerization of Flexible Phosphorescent Polymer Gels.

A general approach to constructing room temperature phosphorescence (RTP) materials involves the incorporation of a phosphorescent emitter into a rigid host or polymers with high glass transition temperature. However, these materials often suffer from poor processability and suboptimal mechanical properties, limiting their practical applications. In this work, we developed benzothiadiazole-based dialkene (BTD-HEA), a multifunctional phosphorescent emitter with a remarkable yield of intersystem crossing (ΦISC, 99.83 %). Its high triplet exciton generation ability and dialkene structure enable BTD-HEA to act as a photoinitiator and crosslinker, efficiently initiating the polymerization of various monomers within 120 seconds. A range of flexible phosphorescence gels, including hydrogels, organogels, ionogels, and aerogels were fabricated, which exhibit outstanding stretchability and recoverability. Furthermore, the unique fluorescent-phosphorescent colorimetric properties of the gels provide a more sensitive method for the visual determination of the polymerization process. Notably, the phosphorescent emission intensity of the hydrogel can be increased by the formation of ice, allowing for the precise detection of hydrogel freezing. The versatility of this emitter paves the way for fabricating various flexible phosphorescence gels with diverse morphologies using microfluidics, film-shearing, roll coating process, and two/three-dimensional printing, showcasing its potential applications in the fields of bioimaging and bioengineering.

Multi‐Functional Integration of Phosphor, Initiator, and Crosslinker for the Photo‐Polymerization of Flexible Phosphorescent Polymer Gels

AbstractA general approach to constructing room temperature phosphorescence (RTP) materials involves the incorporation of a phosphorescent emitter into a rigid host or polymers with high glass transition temperature. However, these materials often suffer from poor processability and suboptimal mechanical properties, limiting their practical applications. In this work, we developed benzothiadiazole‐based dialkene (BTD‐HEA), a multifunctional phosphorescent emitter with a remarkable yield of intersystem crossing (ΦISC, 99.83 %). Its high triplet exciton generation ability and dialkene structure enable BTD‐HEA to act as a photoinitiator and crosslinker, efficiently initiating the polymerization of various monomers within 120 seconds. A range of flexible phosphorescence gels, including hydrogels, organogels, ionogels, and aerogels were fabricated, which exhibit outstanding stretchability and recoverability. Furthermore, the unique fluorescent‐phosphorescent colorimetric properties of the gels provide a more sensitive method for the visual determination of the polymerization process. Notably, the phosphorescent emission intensity of the hydrogel can be increased by the formation of ice, allowing for the precise detection of hydrogel freezing. The versatility of this emitter paves the way for fabricating various flexible phosphorescence gels with diverse morphologies using microfluidics, film‐shearing, roll coating process, and two/three‐dimensional printing, showcasing its potential applications in the fields of bioimaging and bioengineering.

Achieving Efficient Dark Blue Room‐Temperature Phosphorescence with Ultra‐Wide Range Tunable‐Lifetime

Tunable‐lifetime room‐temperature phosphorescence (RTP) materials have been widely studied due to their broad applications. However, only few reports have achieved wide‐range lifetime modulation. In this work, ultra‐wide range tunable‐lifetime efficient dark blue RTP materials were realized by doping methyl benzoate derivatives into polyvinyl alcohol (PVA) matrix. The phosphorescence lifetimes of the doped film can be increased from 32.8 ms to 1925.8 ms. Such wide range of phosphorescence lifetime modulation is extremely rare in current reports. Moreover, the phosphorescence emission of the methyl 4‐hydroxybenzoate‐doped film is located in the dark blue region and the phosphorescence quantum yield reaches as high as 15.4%, which broadens their applications in organic optoelectronic information. Further studies demonstrated that the reason for the tunable lifetime was that the magnitude of the electron‐donating ability of the substituent group modulates the HOMO‐LUMO and singlet‐triplet energy gap of methyl benzoate derivatives, as well as the ability to non‐covalent interactions with PVA. Moreover, the potential applications of luminescent displays and optical anti‐counterfeiting of these high‐performance dark blue RTP materials have been conducted.

Achieving Efficient Dark Blue Room-Temperature Phosphorescence with Ultra-Wide Range Tunable-Lifetime.

Tunable-lifetime room-temperature phosphorescence (RTP) materials have been widely studied due to their broad applications. However, only few reports have achieved wide-range lifetime modulation. In this work, ultra-wide range tunable-lifetime efficient dark blue RTP materials were realized by doping methyl benzoate derivatives into polyvinyl alcohol (PVA) matrix. The phosphorescence lifetimes of the doped film can be increased from 32.8 ms to 1925.8 ms. Such wide range of phosphorescence lifetime modulation is extremely rare in current reports. Moreover, the phosphorescence emission of the methyl 4-hydroxybenzoate-doped film is located in the dark blue region and the phosphorescence quantum yield reaches as high as 15.4%, which broadens their applications in organic optoelectronic information. Further studies demonstrated that the reason for the tunable lifetime was that the magnitude of the electron-donating ability of the substituent group modulates the HOMO-LUMO and singlet-triplet energy gap of methyl benzoate derivatives, as well as the ability to non-covalent interactions with PVA. Moreover, the potential applications of luminescent displays and optical anti-counterfeiting of these high-performance dark blue RTP materials have been conducted.