Phosphorescence Characteristics Research Articles

Circularly Polarized Room Temperature Phosphorescence through Twisting-Induced Helical Structures from Polyvinyl Alcohol-Based Fibers Containing Hydrogen-Bonded Dyes.

Room temperature phosphorescence (RTP) materials have garnered significant attention owing to its distinctive optical characteristics and broad range of potential applications. However, the challenge remains in producing RTP materials with more simplicity, versatility, and practicality on a large scale, particularly in achieving chiral signals within a single system. Herein, we show that a straightforward and effective combination of wet spinning and twisting technique enables continuously fabricating RTP fibers with twisting-induced helical chirality. By leveraging the hydrogen bonding interactions between polyvinyl alcohol (PVA) and quinoline derivatives, along with the rigid microenvironment provided by PVA chains, typically, Q-NH2@PVA fiber demonstrates outstanding phosphorescent characteristics with RTP lifetime of 1.08 s and phosphorescence quantum yield of 24.6 %, and the improved tensile strength being 1.7 times than pure PVA fiber (172±5.82 vs 100±5.65 MPa). Impressively, the transformation from RTP to circularly polarized room temperature phosphorescence (CP-RTP) is readily achieved by imparting left- or right-hand helical structure through simply twisting, enabling large-scale production of chiral Q-NH2@PVA fiber with dissymmetry factor of 10-2. Besides, an array of displays and encryption patterns are crafted by weaving or seaming to exemplify the promising applications of these PVA-based fibers with outstanding adaptivity in cutting-edge anti-counterfeiting technology.

Circularly Polarized Room Temperature Phosphorescence through Twisting‐Induced Helical Structures from Polyvinyl Alcohol‐Based Fibers Containing Hydrogen‐Bonded Dyes

AbstractRoom temperature phosphorescence (RTP) materials have garnered significant attention owing to its distinctive optical characteristics and broad range of potential applications. However, the challenge remains in producing RTP materials with more simplicity, versatility, and practicality on a large scale, particularly in achieving chiral signals within a single system. Herein, we show that a straightforward and effective combination of wet spinning and twisting technique enables continuously fabricating RTP fibers with twisting‐induced helical chirality. By leveraging the hydrogen bonding interactions between polyvinyl alcohol (PVA) and quinoline derivatives, along with the rigid microenvironment provided by PVA chains, typically, Q‐NH2@PVA fiber demonstrates outstanding phosphorescent characteristics with RTP lifetime of 1.08 s and phosphorescence quantum yield of 24.6 %, and the improved tensile strength being 1.7 times than pure PVA fiber (172±5.82 vs 100±5.65 MPa). Impressively, the transformation from RTP to circularly polarized room temperature phosphorescence (CP‐RTP) is readily achieved by imparting left‐ or right‐hand helical structure through simply twisting, enabling large‐scale production of chiral Q‐NH2@PVA fiber with dissymmetry factor of 10−2. Besides, an array of displays and encryption patterns are crafted by weaving or seaming to exemplify the promising applications of these PVA‐based fibers with outstanding adaptivity in cutting‐edge anti‐counterfeiting technology.

Evidence of Short-Lived High-Energy Emissive State and Triplet Character of the Self-Trapped Exciton in Cs3Cu2I5 Perovskite.

Cs3Cu2I5 perovskite displays a Stokes-shifted photoluminescence (PL) at 445 nm, attributed to the self-trapped excitons (STEs). Unlike that observed in other perovskite materials, the free-exciton emission is not evidenced in this case. Herein, we reveal the existence of a short-lived high-energy emission centered around 375 nm through the reconstruction of time-resolved emission spectra (TRES), which is independent of the shape/size of Cs3Cu2I5 perovskite. This high-energy emission is proposed to originate from the free-exciton-derived distorted S1 state of the 0D Cs3Cu2I5 moiety. Moreover, STE PL (∼445 nm) was found to have phosphorescence characteristics. Theoretical calculation confirms a facile intersystem crossing at the Franck-Condon geometry, indicating the high lifetime of the STE and its triplet nature. The existence of a high-energy emissive state and the phosphorescent nature of the STE PL band provide valuable insights that could advance our understanding of the photophysics in these materials.

Dual-channel mechano-phosphorescence: a combined locking effect with twisted molecular structures and robust interactions

Organic mechanoluminescence materials, featuring dual emission and ultralong phosphorescence characteristics, exhibit significant potential for applications in real-time stress sensing, pressure-sensitive lighting, advanced security marking techniques, and material breakage monitoring. However, due to immature molecular design strategies and unclear luminescence mechanisms, these materials remain rarely reported. In this study, we propose a valuable molecular design strategy to achieve dual-channel mechano-phosphorescence. By introducing the arylphosphine oxide group into a highly twisted molecular framework, enhanced intra- and intermolecular interactions could be achieved within rigid structures, leading to dual-channel mechanoluminescence with greatly promoted ultralong phosphorescence. Further investigations reveal the substantial boosting effect of intra- and intermolecular interactions on mechanoluminescence and ultralong phosphorescence properties by locking the highly twisted molecular skeleton. This work provides a concise and guiding route to develop novel smart responsive luminescence materials for widespread applications in material science.

Covalently hybridized carbon dots@mesoporous silica nanobeads as a robust and versatile phosphorescent probe for time-resolved biosensing and bioimaging.

Phosphorescence analyses have attracted broad attention due to their remarkable merits of the elimination of auto-fluorescence and scattering light. However, it remains a great challenge to develop novel materials with uniform size and morphology, stability, long lifetime, and aqueous-phase room temperature phosphorescence (RTP) characteristics. Herein, monodisperse and uniform RTP nanobeads were fabricated by an in situ covalent hybridization of carbon dots (CDs) and dendritic mesoporous silicon nanoparticles (DMSNs) via silane hydrolysis. The formation of Si-O-C and Si-C/N covalent bonds is beneficial for the fixation of vibrations and rotations of the luminescent centers. Specially, the nanopores of DMSNs provide a confined area that can isolate the triplet state of CDs from water and oxygen and thus ensure the occurrence of aqueous-phase RTP with an ultra-long lifetime of 1.195 s (seen by the naked eye up to 9 seconds). Through surface modifying folic acid (FA), CDs@DMSNs can serve as a probe to distinguish different cell lines that feature varying FA receptor expression levels. In addition, taking MCF-7 as the model, highly sensitive and quantitative detection (linear range: 103-106 cells per mL) has been achieved via an RTP probe. Furthermore, their potential applications in cellular and in vivo time-gated phosphorescence imaging have been proposed and demonstrated, respectively. This work would provide a new route to design CD-based RTP composites and promote their further applications in the medical and biological fields.

Cell-penetrating peptides noncovalently modified red phosphorescent nanoparticles for high-efficiency imaging.

The application of long-lived phosphorescence probes in time-resolved luminescence imaging is limited by their low quantum yield in aqueous solutions. However, sensitization of thermally activated delayed fluorescence (TADF) materials can compensate for this limitation while addressing the issue of insufficient proportion of their own long lifetime. In this study, we utilized the characteristics of phosphorescence and TADF materials simultaneously by doping the receptor iridium complex PMD-Ir into the donor TADF polymer PCzDP-20 through donor-receptor doping method, and successfully prepared highly efficient red phosphorescent nanoparticles. The quantum yield of the nanoparticles obtained by this method reaches up to 30%, and the luminescence lifetime can reach several thousand nanoseconds. Additionally, due to the low concentration doping of PMD-Ir, the risk of transition metal toxicity is greatly reduced. Furthermore, we used non-covalent modification with amphiphilic cell-penetrating peptides (CPPs) to increase the cell membrane permeability of the nanoparticles. The CPPs modified nanoparticles achieve in vivo confocal imaging of zebrafish and intracellular time-resolved imaging by its significantly improved bioimaging capabilities. The functional nanoparticles designing method fully utilizes the characteristics of PMD-Ir, PCzDP-20, and CPPs, solving the problems of low quantum yield and poor membrane permeability of Ir-complex nanoparticles. This will greatly promote the development of time-resolved luminescence imaging.

Unraveling Ultralong Phosphorescence in Ar2PO(H): n(O) → σ*(P-C) Transitions in Ar2PO(H) Stabilize Triplet States Better than n(P) → σ*(P-C) in Ar3P

Herein, we report the crystallization-induced persistent room-temperature phosphorescence (CIpRTP) characteristics of simple diarylphosphine oxides 1, 2, and 3. Under ambient conditions, crystalline solids of 1, 2, and 3 show photoluminescence (PL) lifetime of more than 100 ms. At 77 K, they exhibit a PL lifetime of nearly a second. Replacing one of the aryl moieties in Ar3P═O with hydrogen creates more space for intermolecular interactions in Ar2P═O (H); consequently, the latter shows better PL quantum yield (PLQY) than the former. The PLQYs of these compounds are tuned systematically by varying the steric perturbation around the phosphorus center. Detailed analysis of the crystal structure of these compounds revealed that the intermolecular interactions play a crucial role in stabilizing the triplet state in the solid state and bestowing them with CIpRTP. Thin films of these compounds do not show pRTP, further affirming that the intermolecular interactions indeed play a crucial role in stabilizing the triplet state. In the solution state, these compounds show ultraviolet fluorescence (λem ≈ 305 nm) with a small Stokes shift of ∼3200 cm–1 and narrow bandwidth (FWHM: 37, 35, and 33 nm for 1, 2, and 3, respectively). The calculated SOC (⟨T1|Ĥ|S0⟩) matrix element for 1, 2, and 3 is significantly lower than the value estimated for triarylphosphines; thus, the former show ultralong phosphorescence compared to the latter. Furthermore, the n(O) → σ*(P-C) transition plays a crucial role in controlling the optical features in these compounds.

Scissor-like Au4Cu2 Cluster with Phosphorescent Mechanochromism and Thermochromism

Reaction of [Au(tht)2](ClO4) (tht = tetrahydrothiophene), [Cu(CH3CN)4](ClO4), 3,6-di-tert-butyl-1,8-diethynyl-9H-carbazole (H3decz), and bis(2-diphenylphosphinophenyl)ether (POP) in the presence of triethylamine (NEt3) gave the cluster complex Au4Cu2(decz)2(POP)2 as yellow crystals. As revealed by X-ray crystallography, the Au4Cu2 cluster exhibits scissor-like structure sustained by two decz and two POP ligands and stabilized by Au-Cu and Au-Au interactions. The Au4Cu2 cluster shows bright yellow to orange photoluminescence upon irradiation at >300 nm, arising from 3[π (decz)→5d (Au)] 3LMCT (ligand-to-metal charge transfer) and 3[π→π* (decz)] 3IL (intraligand) triplet states as revealed by theoretical and computational studies. When it is mechanically ground, reversible phosphorescence conversion from yellow to red is observed owing to more compact molecular packing and thus stronger intermetallic interaction. Variable-temperature luminescence studies reveal that it displays distinct red-shifts of the emission whether the temperature is elevated or lowered from ambient temperature, suggestive of exceptional thermochromic phosphorescence characteristics.

Modulating Narrow-Band Phosphorescence of Pt2Au4 Cluster Complexes by Differently Positioned Bis(acetylide)-Naphthalene Linkers

To modulate phosphorescent characteristics of Pt2Au4 complexes with differently positioned bis(acetylide)naphthalene as a bridging ligand, four isomeric Pt2Au4 complexes (1–4) linked by 1,4-bis(acetylide)naphthalene (1), 1,5-bis(acetylide)naphthalene (2), 2,6-bis(acetylide)naphthalene (3), and 2,7-bis(acetylide)naphthalene (4) are elaborately designed and prepared. The Pt2Au4 complexes are strongly phosphorescent with the quantum yields as high as 52% in CH2Cl2 solutions, in strikingly contrast to weak phosphorescence of bis(acetylide)naphthalene-linked Pt2 precursors. After the formation of Pt2Au4 cluster structures, the increased molecular rigidity dramatically suppresses nonradiative relaxation, which becomes less competitive in contrast to the radiative relaxation of the emitting state, thus resulting in a remarkable enhancement of the quantum yields. Depending on the positions of bis(acetylide) groups attached to naphthalene rings, the phosphorescence of Pt2Au4 isomers in CH2Cl2 solutions follows 1 (640 nm) → 2 (582 nm) → 3 (567 nm) → 4 (529 nm) to show progressive blue shifts. As demonstrated by photophysical and theoretical studies, vibronic-structured narrow-band emission with a full width at half maxima (fwhm) of 707–1073 cm–1 is primarily ascribable to ligand-centered triplet states localized at bis(acetylide)naphthalenes, which is dramatically activated upon the formation of the Pt2Au4 cluster because the energy harvested by two PtAu2 cluster moieties is effectively transferred to bridging bis(acetylide)naphthalene. Taking advantage of Pt2Au4 complexes 1–4 as phosphorescent emitters, solution-processed OLEDs achieve narrow-band electroluminescence with peak external quantum efficiency of 11.0% for red-emitting complex 1 (fwhm = 45 nm or 1058 cm–1), 9.4% for orange-emitting complex 2 (fwhm = 33 nm or 960 cm–1), 13.7% for yellow-emitting complex 3 (fwhm = 33 nm or 1029 cm–1), and 15.2% for green-emitting complex 4 (fwhm = 24 nm or 848 cm–1).

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.

F, N co-doped carbon nanomaterials for multi-level information encryption: Room-temperature phosphorescence and solid-state fluorescence

The non-radiative transition of triplet excitons limits the emission of room-temperature phosphorescence (RTP). In this paper, F, N co-doped carbon nanomaterials including carbon dot solutions (L-CDs) with cyan fluorescence and solid-state carbon nanowires (S-CNWs) with yellow fluorescence were successfully prepared by the one-pot hydrothermal method. Interestingly, L-CDs@PVA composites with green RTP were obtained by mixing L-CDs with PVA. The RTP production was attributed to F, N related heteroatomic functional groups on the surface of L-CDs. The C-N, CN bonds form lone electron pairs, which promote the electron transition from n→π∗. The F doping reduces the energy gap from the single to the triplet state, which facilitates the inter-system crossing (ISC) process and increases the radiative transition of the triplet exciton to produce RTP. In addition, PVA forms abundant hydrogen bonds with L-CDs to effectively immobilize the luminescence center and isolate atmospheric oxygen, so that L-CDs@PVA has stable phosphorescence emission at room temperature and this phosphorescence is reversible in dry and wet states. In contrast, S-CNWs displayed solid-state yellow fluorescence, but no phosphorescence even though doped into the PVA matrix (S-CNWs@PVA). Therefore, based on the different characteristics of fluorescence and phosphorescence of L-CDs and S-CNWs, a complex, multi-level information encryption method is proposed and the potential applications of S-CNWs powder for fingerprint recording are explored.

Facile Preparation Strategy of Novel Carbon Dots with Aggregation‐Induced Emission and Room‐Temperature Phosphorescence Characteristics

AbstractAs one of the most promising fluorescent nanomaterials, carbon dots (CDs) are extensively studied. Nevertheless, one‐pot synthesis methods for CDs with both dual emission aggregation‐induced emission (AIE) and room‐temperature phosphorescence (RTP) could lead to significant breakthrough in extensive application fields. Herein, a new class of CDs (E‐CCDs) with reversible luminescence (blue dissolved fluorescence and red AIE) and RTP behavior is obtained with an eco‐friendly, low‐cost one‐pot solvothermal method. E‐CCDs exhibit dual fluorescence emission at 460 (Em‐1) and 600 nm (Em‐2), which is related to different emission centers. The addition of cyanic acid enhances the RTP behavior with a lifetime of 1.17 s, which lasts for ≈9 s to the naked eye. Based on the unique fluorescence and phosphorescence characteristics of CDs, E‐CCDs can be potentially used for fingerprint detection and information encryption.

Preparation of transparent photoluminescence smart window by integration of rare-earth aluminate nanoparticles into recycled polyethylene waste.

Novel photoluminescent nanocomposite sheets were prepared for simple commercial manufacturing of transparent and luminous photochromic smart windows. A simple physical integration of lanthanide-doped strontium aluminium oxide (LdSAO) nanoparticles into recycled polyethylene (PE) waste produced a smart nanocomposite with persistent phosphorescence and photochromic properties. Because the nanoparticle form of LdSAO is important for developing transparent materials, LdSAO nanoparticles were well dispersed in the PE matrix. Both the morphologies and chemical compositions of the LdSAO nanoparticles and LdSAO-containing luminescent PE sheets were investigated. Both LdSAO-free and photoluminescent PE sheets were colourless in normal daylight. However the LdSAO-containing PE luminescent samples only exhibited a brilliant green colour under ultraviolet (UV) light and a greenish-yellow colour in the dark as verified by Commission Internationale de l'éclairage laboratory parameters. Both absorbance and emission bands were monitored at 377 and 436/517 nm, respectively. The LdSAO-containing PE luminescent sheets were compared with the LdSAO-free sample using both photoluminescence spectroscopy and for their mechanical properties and were found to have improved scratch resistance, UV protection, and superhydrophobic activity. Due to the added LdSAO, photoluminescence, decay, and lifetime spectral tests confirmed its photochromic fluorescence and long-lasting phosphorescence characteristics. The PE@LdSAO nanocomposite sheets displayed UV protection, photostability, hydrophobicity, and excellent durability compared with the blank LdSAO-free PE sheet.

Low Blue Dose Photodynamic Therapy with Porphyrin-Iron Oxide Nanoparticles Complexes: In Vitro Study on Human Melanoma Cells.

The purpose of this study was to investigate the effectiveness in photodynamic therapy of iron oxide nanoparticles (γ-Fe2O3 NPs), synthesized by laser pyrolysis technique, functionalized with 5,10,15,20-(Tetra-4-sulfonatophenyl) porphyrin tetraammonium (TPPS) on human cutaneous melanoma cells, after only 1 min blue light exposure. The efficiency of porphyrin loading on the iron oxide nanocarriers was estimated by using absorption and FTIR spectroscopy. The singlet oxygen yield was determined via transient characteristics of singlet oxygen phosphorescence at 1270 nm both for porphyrin functionalized nanoparticles and rose bengal used as standard. The irradiation was performed with a LED (405 nm, 1 mW/cm2) for 1 min after melanoma cells were treated with TPPS functionalized iron oxide nanoparticles (γ-Fe2O3 NPs_TPPS) and incubated for 24 h. Biological tests revealed a high anticancer effect of γ-Fe2O3 NPs_TPPS complexes indi-cated by the inhibition of tumor cell proliferation, reduction of cell adhesion, and induction of cell death through ROS generated by TPPS under light exposure. The biological assays were combined with the pharmacokinetic prediction of the porphyrin.

Iridium(III) Complexes with [-2, -1, 0] Charged Ligand Realized Deep-Red/Near-Infrared Phosphorescent Emission.

A series of [-2, -1, 0] charged-ligand based iridium(III) complexes of [Ir(bph)(bpy)(acac)] (1), [Ir(bph)(2MeO-bpy)(acac)] (2), [Ir(bph)(2CF3 -bpy)(acac)] (3), [Ir(bph)(bpy)(2t Bu-acac)] (4) and [Ir(bph)(bpy)(CF3 -acac)] (5), which using biphenyl as dianionic ligand [-2], acetylacetone (or its derivatives) as monoanionic ligand [-1], and 2,2'-bipyridine (or its derivatives) as neutral ligand [0] were designed and synthesized. The chemical structures were well characterized. All of the ligands have simple chemical structures, thus further making the complexes have excellent thermal stability and are easy to sublimate and purify. Phosphorescent characteristics with short emission lifetime were demonstrated for these emitters. Notably, all of the complexes exhibit remarkable deep red/near infrared emission, which is quite different from the reported [-1, -1, -1] charged-ligand based iridium(III) complexes. The photophysical properties of these complexes are regularly improved by introducing electron-donating or -withdrawing groups into [-1] or [0] charged-ligand. The related organic light-emitting diodes exhibited deep red/near infrared emission with acceptable external quantum efficiency and low turn-on voltage (<2.6 V). This work provides a new idea for the construction of new type phosphorescent iridium(III) emitters with different valence states of [-2, -1, 0] charged ligands, thus offering new opportunities and challenges for their optoelectronic applications.

Rational design of pyrrole derivatives with aggregation-induced phosphorescence characteristics for time-resolved and two-photon luminescence imaging

Pure organic room-temperature phosphorescent (RTP) materials have been suggested to be promising bioimaging materials due to their good biocompatibility and long emission lifetime. Herein, we report a class of RTP materials. These materials are developed through the simple introduction of an aromatic carbonyl to a tetraphenylpyrrole molecule and also exhibit aggregation-induced emission (AIE) properties. These molecules show non-emission in solution and purely phosphorescent emission in the aggregated state, which are desirable properties for biological imaging. Highly crystalline nanoparticles can be easily fabricated with a long emission lifetime (20 μs), which eliminate background fluorescence interference from cells and tissues. The prepared nanoparticles demonstrate two-photon absorption characteristics and can be excited by near infrared (NIR) light, making them promising materials for deep-tissue optical imaging. This integrated aggregation-induced phosphorescence (AIP) strategy diversifies the existing pool of bioimaging agents to inspire the development of bioprobes in the future.

Influence of Guest/Host Morphology on Room Temperature Phosphorescence Properties of Pure Organic Doped Systems.

Guest/host phosphorescence materials have attracted much attention; traditionally, researchers have focused on the influence of the electronic properties and energy levels of the molecules on the phosphorescence activities. However, the effects of the morphology on the phosphorescence properties are ignored. Herein, three isoquinoline guests with different aliphatic rings and three hosts are selected to construct guest/host materials. Experimental results confirm that the guests are dispersed in the host in the form of clusters. More importantly, the morphologies of the guest/host directly affect the phosphorescence properties. In these systems, the guests have strong intermolecular interactions, which are beneficial to stabilize the triplet excitons; meanwhile, the hosts should have weak intermolecular interactions with easily changed morphology to accept the guest clusters, which synergistically ensure that the doped materials have excellent RTP properties. This is the first work focusing on the effect of molecular morphology on the phosphorescence characteristics of guest/host systems.

Recent Advances of Cocrystals with Room Temperature Phosphorescence

AbstractOrganic phosphorescent materials have attracted wide attention in recent years owing to their opportunities in various functional applications. Through appropriate molecular design strategies and synthetic perspectives to modulate their weak spin–orbit coupling, highly active triplet excitons, and ultrafast deactivation, the organic phosphors can be endowed with long‐lived room temperature phosphorescence (RTP) characteristics. Organic cocrystals constructed by noncovalent intermolecular interactions (hydrogen and halogen bonding, π–π stacking and so on) are provoking wide interest due to their unexpected and multifaceted phosphorescence properties and their applications. In this review, research on organic cocrystals with RTP based on their interactions is described, revealing their structure–property relationships. Furthermore, current accomplishments, restrictions, and viewpoints along with some guidance for their further study are discussed.

Millisecond Time-scale Photoluminescence of B–N-doped Tetrathienonaphthalene with Borane/Amine Substituents

BN-doped polycyclic aromatic hydrocarbons (PAHs) have attracted numerous attentions because of their fascinating optical and electronic properties. In this work, a series of electron-donor (amine)- and -acceptor (borane)-functionalized BN-doped polycyclic aromatic hydrocarbons were prepared to study the substituents' effect on the photophysical properties. As a result, the compound with both donor and acceptor, BN, exhibits both local emission (LE) and charge-transfer emission (CT) in polar solvents. Especially, the CT emission with a longer wavelength revealed a lifetime as long as millisecond time scale at room temperature, indicating typical phosphorescence characteristics. Low-temperature photoluminescent (PL) spectroscopy and a theoretical study were conducted to help to interpret this phenomenon, and it turned out to be the lowering of the S1 energy level of BN which makes the intersystem crossing favorable. Furthermore, fluoride anion titration experiments exhibit the application potential of the dual-emission phenomenon of BN for ratiometric sensory materials.

Phosphorescence of thermally altered human bone

Bone has photoluminescent characteristics that can aid the analysis of thermally altered human skeletal remains as part of the forensic anthropological investigation. Photoluminescence stands collectively for fluorescence and phosphorescence. Because the difference in lifetime between fluorescence and phosphorescence is usually in the range of nano- to microseconds, it is only possible to visually determine whether bone phosphoresces when the lifetime is long enough to be observed. For this study, a distinction was made between long-decay and short-decay phosphorescence. So far, it was unknown whether (thermally altered) human bone emits long-decay phosphorescence after being illuminated and, thus, whether phosphorescence contributes to the observed photoluminescence. If so, whether the observable phosphorescence is dependent on temperature, exposure duration, surrounding medium, bone type, skeletal element, and excitation light and could aid the temperature estimation of heated bone fragments. In this study, bone samples were subjected to heat in the range of from room temperature to 900 °C for various durations in either air or adipose as surrounding medium. In addition, different skeletal elements of a human cadaver were recollected after cremation in a crematorium. Both sample collections were illuminated with light of different bandwidths and visually inspected for phosphorescence and photoluminescence. The samples were scored by means of a scoring index for the intensity of long-decay phosphorescence and photographically documented. The results show that thermally altered human bone fragments do phosphoresce. The observed phosphorescence is more dependent on temperature than on exposure duration, surrounding medium or skeletal element. Of the used wavelength bands, ultraviolet light provided the most temperature-related information, showing changes in both phosphorescence intensity and emission spectrum. Long-decay phosphorescence and fluorescence with short-decay phosphorescence coincide; however, there are also temperature-dependent differences. It is therefore concluded that phosphorescence contributes to the observable photoluminescence and that the visibly observable phosphorescent characteristics can aid the temperature estimation of cremated human skeletal fragments.