Long-lived Room-temperature Phosphorescence Research Articles

A Sodium Metal-Organic Framework with Deep Blue Room-Temperature Phosphorescence.

It is a great challenge to manufacture room-temperature blue long afterglow phosphorescent materials adapted to environmental conditions. Herein, an Na-based metal-organic framework (MOF) was constructed using Na+ and 1H-1,2,4-triazole-3,5-dicarboxylic acid, which exhibits long-lived of 378.9 ms, deep blue and room-temperature phosphorescence, meanwhile possesses the visible blue afterglow for 3~6 seconds after removing excitation light source. The three-dimensional coordination bonds network provided by Na-based MOF protects the organic ligands intrinsic hydrogen bond network, resulting in the phosphor lifetime and residual color remaining unchanged in different gas atmospheres. Furthermore, first-principles time-dependent density functional theory reveals that the rigid Na-based MOF structure can limit the rotation and vibration of the room-temperature phosphorescent organic ligands. This limitation results in the suppression of non-radiative decay for both singlet and triplet excitons, promotes intersystem crossing, and increases the rate of radiative decay, ultimately achieving long-lived room-temperature phosphorescence.

Room-temperature phosphorescence of defect-engineered silica nanoparticles for high-contrast afterglow bioimaging

Room-temperature phosphorescence (RTP) has tremendous potential in optics and photonics. Unlike fluorescence, RTP has substantial afterglow signals even after the excitation light is removed, which allows for extended acquisition times and higher signal-to-noise ratio under time-gated bioimaging. However, conventional RTP materials, both metal-containing and metal-free organic compounds, typically have limited photostability and inherent toxicity, making them unsuitable for long-term biological applications. Here, we report metal- and organic fluorophore-free silica nanoparticles (SNPs) that facilitate long-lived phosphorescence and exhibit RTP for high-contrast bioimaging. Polycondensation of silicon precursors and silyl biphenyls forms biphenyl-doped SNPs (bSNPs), and thermal decomposition of biphenyl moieties generates optically active defects in the biphenyl-bonded silicate network. The calcined bSNPs (C-bSNPs) have RTP-related biphenyl defects composed of carbon impurities, corresponding to spectroscopic measurements and ab initio calculations. Facile surface functionalization of defect-engineered C-bSNPs with tumor-targeting peptides while maintaining long-lived RTP allows for tissue autofluorescence-free in vivo bioimaging for cancer diagnosis, surpassing the limitations of continuous-wave imaging.

Visible-light-excited robust room-temperature phosphorescence of dimeric single-component luminophores in the amorphous state

Organic room temperature phosphorescence (RTP) has significant potential in various applications of information storage, anti-counterfeiting, and bio-imaging. However, achieving robust organic RTP emission of the single-component system is challenging to overcome the restriction of the crystalline state or other rigid environments with cautious treatment. Herein, we report a single-component system with robust persistent RTP emission in various aggregated forms, such as crystal, fine powder, and even amorphous states. Our experimental data reveal that the vigorous RTP emissions rely on their tight dimers based on strong and large-overlap π-π interactions between polycyclic aromatic hydrocarbon (PAH) groups. The dimer structure can offer not only excitons in low energy levels for visible-light excited red long-lived RTP but also suppression of the nonradiative decays even in an amorphous state for good resistance of RTP to heat (up to 70 °C) or water. Furthermore, we demonstrate the water-dispersible nanoparticle with persistent RTP over 600 nm and a lifetime of 0.22 s for visible-light excited cellular and in-vivo imaging, prepared through the common microemulsion approach without overcaution for nanocrystal formation.

Single component long-lived dynamic room temperature phosphorescence with large-scale preparation and visible light excitation

A pure organic room temperature phosphorescence (PORTP) luminogen named as DCP was successfully prepared and showed long room temperature phosphorescence (RTP) and afterglow lifetimes (3 ms and 4 s in sequence). Meanwhile, DCP showed high fluorescence (0.14) and RTP (0.39) quantum yields in crystalline state, simultaneously presented visible light excitation and dynamic RTP. By host-guest doping and optimization, Urea/DCP doping system emitted blue RTP, with RTP and afterglow lifetimes of 341 ms of 5 s in turn. Crystal analysis and theoretical calculations indicated H stacking, large spin orbit coupling constant, and small energy gap between the lowest singlet and triplet states result in long RTP lifetime and high quantum yield for DCP. Based on long phosphorescence emission, an advanced anti-counterfeiting pattern was constructed. As far as we know, it is the first report that such small molecules containing 3, 5-dicyanopyridine show long-lived RTP in both crystalline state and doping system. In this paper, not only ultralong and blue PORTP materials with the advantage of large-scale preparation, but also single component dynamic RTP, and RTP of visible light excitation were achieved.

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.

Ground-State Orbital Descriptors for Accelerated Development of Organic Room-Temperature Phosphorescent Materials.

Organic materials with room-temperature phosphorescence (RTP) are in high demand for optoelectronics and bioelectronics. Developing RTP materials highly relies on expert experience and costly excited-state calculations. It is a challenge to find a tool for effectively screening RTP materials. Herein we first establish ground-state orbital descriptors (πFMOs ) derived from the π-electron component of the frontier molecular orbitals to characterize the RTP lifetime (τp ), achieving a balance in screening efficiency and accuracy. Using the πFMOs , a data-driven machine learning model gains a high accuracy in classifying long τp , filtering out 836 candidates with long-lived RTP from a virtual library of 19,295 molecules. With the aid of the excited-state calculations, 287 compounds are predicted with high RTP efficiency. Impressively, experiments further confirm the reliability of this workflow, opening a novel avenue for designing high-performance RTP materials for potential applications.

Metal ion-manipulated afterglow on rhodamine 6G derivative-doped room-temperature phosphorescent PVA films.

The long-lived room-temperature phosphorescence (RTP) originating from thiophene boronate polyvinyl alcohol (PVA) has enabled the creation of metal-ion-responsive RTP films doped with spirolactam ring-containing rhodamine 6G (1). In this study, RTP-active PVA films, namely, TDB@PVA and ATB@PVA, were prepared through boronate esterification of thiophene-2,5-diboronic acid (TDB) and 5-acetylthiophene-2-boronic acid (ATB) with the diol units of PVA. The delayed emission properties were evaluated, revealing an emission band at 477nm with a turquoise afterglow for TDB@PVA and at 510nm with a green afterglow for ATB@PVA after UV light irradiation ceased. The photophysical properties were assessed using TD-DFT and DFT calculations at the B3LYP/cc-pVDZ level. N-(rhodamine-6G)lactam dye with a salicylimine unit (1) was doped into the RTP-based PVA films, producing a multicolored afterglow upon the addition of metal ions. This phenomenon is explained by a triplet-to-singlet Förster-type resonance energy transfer process from the cross-linked thiophene boronate in PVA to the metal-ion-activated colored form of 1. This photophysical feature finds applicability in encryption techniques. Notably, the reversible metal-ligand coordination of 1 in the PVA system enabled a write/erase information process.

Access to long-lived room temperature phosphorescence through auration of 2,1,3-benzothiadiazole.

A series of 2,1,3-benzothiadiazole-Au(I)-L complexes have been synthesised, structurally characterised and investigated for their photophysical properties. These are the first organometallic Au(I) complexes containing a C-Au bond on the highly electron-deficient benzothiadiazole unit. The complexes exhibit solution-phase phosphorescence at room temperature, assigned to the intrinsic triplet state of the benzothiadiazole unit that is efficently populated through its attachment to gold. Comparison with routinely reported Au(I) complexes, which include intervening alkenyl linkers, suggests that previous assignments of their phosphorescence as 1π → π*(CCR) might be incomplete. Our observations affirm that, in addition to the heavy atom effect, breaking symmetry in the involved aryl motif may be of importance in controlling the luminescence properties.

Circularly Polarized Organic Ultralong Room-Temperature Phosphorescence with A High Dissymmetry Factor in Chiral Helical Superstructures.

Long-lived room-temperature phosphorescence (RTP) of organic materials holds a significant potential for optical information. Circularly polarized organic ultralong room-temperature phosphorescence (CP-OURTP) with extremely high dissymmetry factor (glum ) values is even highly demanded and considerably challenging. Here, an effective strategy is introduced to realize CP-OURTP with an emission decay time of 735ms and a glum value up to 1.49, which exceeds two orders of magnitude larger than previous records, through a system composed of RTP polymers and chiral helical superstructures. The system exhibits excellent stability under multiple cycles of photoirradiation and thermal treatment, and is further employed for information encryption based on optical multiplexing. The results are anticipated to lay the foundation for the development of CP-OURTP materials in advanced photonic applications.

Unique Visualization Growth Process of Long-Lived Room Temperature Phosphorescence in Polymer System.

Recently, embedding organic phosphors into the polyvinyl alcohol (PVA) matrix has emerged as a convenient strategy to obtain efficient long-lived room temperature phosphorescence (RTP) via forming strong intermolecular hydrogen bonds with organic phosphors to minimize nonradiative relaxations. Regrettably, it is discovered that PVA is unable to trigger RTP emission when a novel functional phosphor THBE containing six extended biphenyl formaldehyde arms is doped into PVA matrix. Surprisingly, the excellent long-lived RTP emission can be easily obtained by doping THBE into PVA analogs, poly(vinyl alcohol-co-ethylene) (PVA-co-PE). The unique visualization growth process (i.e., white streak generation) of long-lived RTP is observed by UV light-driven aggregation of functional molecules THBE in PVA-co-PE matrix. The phosphorescent intensity of the luminescent film is enhanced by 55 times, from 729 to 40,785 a.u., and its phosphorescence lifetime is increased by 38 times, from 37.08 to 1415.41ms. Due to the dynamically reversible RTP performance, as well as the permeability, flexibility, and wrinkle-free properties of the luminescent film, it can be utilized to create cutting-edge information storage devices.

Modulating Aryl Azide Photolysis: Synthesis of a Room-Temperature Phosphorescent Carboline in Cucurbit[7]uril Host.

Cucurbit[7]uril (CB7), a supramolecular host, is employed to control the pathway of photolysis of an aryl azide in an aqueous medium. Normally, photolysis of aryl azides in bulk water culminates predominantly in the formation of azepine derivatives via intramolecular rearrangement. Remarkably, however, when this process unfolds within the protective confinement of the CB7 cavity, it results in a carboline derivative, as a consequence of a C─H amination reaction. The resulting carboline caged by CB7 reveals long-lived room temperature phosphorescence (RTP) in the solid state, with lifetimes extending up to 2.1 s. These findings underscore the potential of supramolecular hosts to modulate the photolysis of aryl azides and to facilitate novel phosphorescent materials.

Synthesis and properties of long-lived room-temperature phosphorescent liquid crystal polymers based on “Jacketing” effect

Polymerization is one of the most widely used strategies to achiever RTP. To date, various polymer-based RTP materials have been reported. However, how to improve the phosphorescence lifetime of polymer-based RTP materials still needs to be further researched. In this article, we proposed a new strategy to realize long-lived room-temperature phosphorescence by utilizing the “jacketing” effect of mesogen-jacketed liquid crystal polymers. Two polymers PMJ0DFM and PMJ6DFM with different flexible spacer length were synthesized, and their liquid crystal phase structures and photo-physical properties were systematically investigated. PMJ0DFM formed columnar nematic phase while PMJ6DFM formed a more ordered hexagonal columnar phase liquid crystal. For PMJ0DFM without spacer length, due to the strong “Jacketing” effect, the thermal motion of the chromophore was suppressed, and it was also more conducive to the aggregation and planarization of the chromophores. Therefore, PMJ0DFM film showed longer phosphorescence lifetime and more red-shifted phosphorescence spectrum than PMJ6DFM film. The phosphorescence lifetimes of PMJ0DFM and PMJ6DFM were 355 ms and 247 ms, respectively. In addition, we also explored their application in linearly polarized luminescent materials. When oriented, PMJ0DFM and PMJ6DFM film could emit efficient linearly polarized room temperature phosphorescence.

Stepwise taming of triplet excitons via multiple confinements in intrinsic polymers for long-lived room-temperature phosphorescence

Polymeric materials exhibiting room temperature phosphorescence (RTP) show a promising application potential. However, the conventional ways of preparing such materials are mainly focused on doping, which may suffer from phase separation, poor compatibility, and lack of effective methods to promote intersystem crossing and suppress the nonradiative deactivation rates. Herein, we present an intrinsically polymeric RTP system producing long-lived phosphorescence, high quantum yields and multiple colors by stepwise structural confinement to tame triplet excitons. In this strategy, the performance of the materials is improved in two aspects simultaneously: the phosphorescence lifetime of one polymer (9VA-B) increased more than 4 orders of magnitude, and the maximum phosphorescence quantum yield reached 16.04% in halogen-free polymers. Moreover, crack detection is realized by penetrating steam through the materials exposed to humid surroundings as a special quenching effect, and the information storage is carried out by employing the Morse code and the variations in lifetimes. This study provides a different strategy for constructing intrinsically polymeric RTP materials toward targeted applications.

Luminescent Mechanism and Anti-Counterfeiting Application of Hydrophilic, Undoped Room-Temperature Phosphorescent Silicon Nanocrystals.

Silicon nanocrystals (SiNCs) have attracted extensive attention in many advanced applications due to silicon's high natural abundance, low toxicity, and impressive optical properties. However, these applications are mainly focused on fluorescent SiNCs, little attention is paid to SiNCs with room-temperature phosphorescence (RTP) and their relative applications, especially water-dispersed ones. Herein, this work presents water-dispersible RTP SiNCs (UA-SiNCs) and their optical applications. The UA-SiNCs with a uniform particle size of 2.8nm are prepared by thermal hydrosilylation between hydrogen-terminated SiNCs (H-SiNCs) and 10-undecenoic acid (UA). Interestingly, the resultant UA-SiNCs can exhibit tunable long-lived RTP with an average lifetime of 0.85 s. The RTP feature of the UA-SiNCs is confirmed to the n-π* transitions of their surface C═O groups. Subsequently, new dual-modal emissive UA-SiNCs-based ink is fabricated by blending with sodium alginate (SA) as the binder. The customized anticounterfeiting labels are also prepared on cellulosic substrates by screen-printing technique. As expected, UA-SiNCs/SA ink exhibits excellent practicability in anticounterfeiting applications. These findings will trigger the rapid development of RTP SiNCs, envisioning enormous potential in future advanced applications such as high-level anti-counterfeiting, information encryption, and so forth.

1,10-Phenanthroline-5-amine derived N-doped carbon dots for long-lived visible-light-activated room temperature phosphorescence in the matrix and information encryption application

Room temperature phosphorescence (RTP) materials have received a lot of attention. However, it is still a challenge to realize the practical application of RTP excited under visible light. Herein, five different carbon dots (CDs) were prepared using 1,10-phenanthroline-5-amine (Aphen) as the co-carbon source and nitrogen source, and several polymer-based RTP films were prepared by simple doping. It was found that the phosphorescence emission behavior of polymer films was changed by the surface state structure of different CDs. Non-radiative transition of the triplet excitons of Aphen structure on the CDs surface was effectively inhibited by the hydrogen bonding interaction and the fixed domain-limiting effect of the polymer matrix. Meanwhile, the Aphen structure was bound to the CDs through covalent interaction, which further suppressed the molecular vibration, realizing the efficient organic RTP. The phosphorescence lifetime of the prepared ACCDs-PVA films reached 352.88 ms with a photoluminescence quantum yield of 36.7%. In addition, the dye RhB was co-doped in the ACCDs-PVA system to modulate the afterglow color of the materials via the triplet to single-state energy resonance transfer (TS-FRET) process. Finally, we also developed stable ACCDs-EPO RTP material by exploiting the dense three-dimensional network structure and hydrophobic property of the cured epoxy resin (EPO) matrix. The as-constructed long-lived RTP materials can be employed in information encryption.

Ultralong Room-Temperature Phosphorescence with Second-level Lifetime in Water Based on Cyclodextrin Supramolecular Assembly.

Organic solid-state materials with long-lived room-temperature phosphorescence (RTP) emission have been widely developed and applied in many fields, while works in developing solution-phase phosphorescence materials were rarely reported owing to the ultrafast nonradiative relaxation and quenchers from the liquid medium. Herein, we report an ultralong RTP system in water through assembly based on a β-cyclodextrin host and p-biphenylboronic acid guest with a lifetime of 1.03 s under ambient conditions. It is worth noting that the long-lived phosphorescence depends on the host-guest inclusion as well as intermolecular hydrogen bonding interactions, which suppress nonradiative relaxation and avoid quenchers effectively. Furthermore, the addition of fluorescent dyes to the assembly system achieved the tuning of the afterglow color through radiative energy transfer of reabsorption.

Long-lived room-temperature phosphorescent complex of B, N, P co-doped carbon dots and silica for afterglow imaging

Room temperature phosphorescent (RTP) materials based on carbon dots (CDs) have attracted abundant attention in bioimaging owing to their long lifetimes and wide Stokes shift, which can reduce the autofluorescence and light scattering in tissue. Although solid-state RTP CDs have been widely reported at present, long-lived RTP CDs in aqueous solutions still remain a challenge because they are usually quenched by oxygen in water. This work develops a heteroatom doping strategy to synthesize long-lived matrix-free phosphorescent B, N, P co-doped CDs (B, N, P-CDs) with cross-linked structure and rich hydrogen bonding network. B, N, P-CDs have an ultralong phosphorescence lifetime of 1.89 s. Subsequently, the complex of B, N, P co-doped CDs and silica (B, N, P-CDs@SiO2) was further obtained by coating the surfaces of B, N, P-CDs with silica by sol-gel method to further confine their molecular vibrations and rotations, which shows an excellent RTP property in aqueous solution with a phosphorescent lifetime of 1.97 s. In addition, the complex displays good biocompatibility, low cytotoxicity, and ability of phosphorescent labeling cells and organism. All these results extend a potential application of the B, N, P-CDs@SiO2 complex as phosphorescent bioimaging probe.

Adsorption of indole[3, 2-b]carbazole derivatives in the filter paper matrix to realize long-lived room temperature phosphorescence emission

Adsorption of indole[3, 2-b]carbazole derivatives in the filter paper matrix to realize long-lived room temperature phosphorescence emission

Coordination-driven stacking of carbazole-based molecule for dynamic long-lived room temperature phosphorescence

Distinguishing from static room temperature phosphorescence (RTP) materials, time-evolution dynamic RTP still face great challenges. In this work, we obtained two supramolecular coordination polymers [Cd2(CzIP)2(2-MIM)2] (1) and [Zn2(CzIP)4(DMI)2] (2) (CzIP ​= ​5-(carbazol-9-yl) isophthalate, 2-MIM ​= ​2-methylimidazole, DMI ​= ​N, N-Dimethylacetamide). These two compounds have the similar H-aggregation of carbazole fragments but with different overlap degree, but exhibit the different optical performance in phosphorescence lifetimes and stimuli responsive properties. The lifetimes of compounds 1 and 2 is 700.31 and 18.68 ​ms, respectively. Surprisingly, compound 1 exhibits dynamic room temperature phosphorescence with the color change from orange to green over the while delayed time. These results demonstrates that the coordination-tunable stacking behaviors play an important role in the generation of room temperature phosphorescence.

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.