Charge-transfer Complexes Research Articles

Reactivity of polyaniline composites with attractive cyclic nitramines

Composite microcrystals of the nitramines (NAs) RDX, HMX, BCHMX and CL-20 with electrically conductive polyaniline (PANi) are a charge transfer complexes in composite crystals (CACs). The activation energies of thermolysis, Ea, of the pure NAs and their PANi-composites were determined using the Kissinger method, and decomposition processes are discussed. Except for the RDX/PANi CAC, all the other CACs show higher Ea values for decomposition compared to their pure NA counterparts. For all CACs, relationships are specified between the Ea values, on the one hand, and the squares of the detonation velocities, enthalpies of formation, spark energy and impact sensitivities, on the other. The relationships between their low-temperature heats of decomposition, ΔH, from DSC, and their enthalpy of formation, logarithm of impact sensitivity, electric spark energy, as well as detonation energy, are described. The PANi favorably influences the density of the corresponding CAC; surprisingly close linear correlations were found, and explained, between these densities and the Ea values. This presence of PANi strongly increased the electrical spark sensitivity of the CACs in comparison to the base NAs. Based on the results obtained, it can be noted in particular the exceptional desensitization of HMX to impact and the increased sensitivity to electrical spark by coating its crystals with polyaniline.

Charge Transfer Complexes, Based on 2,4-Diethyl-9-oxo-10-(4-heptyloxyphenyl)-9H-thioxanthenium Hexafluorophosphate and Thiazole Derivatives, as Photoinitiators of Holographic Free Radical Photopolymerization

Charge Transfer Complexes, Based on 2,4-Diethyl-9-oxo-10-(4-heptyloxyphenyl)-9H-thioxanthenium Hexafluorophosphate and Thiazole Derivatives, as Photoinitiators of Holographic Free Radical Photopolymerization

A DFT study of gas molecules adsorption on TM-doped PtS2 gas nanosensors

In this study, we examined the adsorption and sensing capabilities of transition metal doped PtS2 monolayers (TM = Co, Cu, Fe, Ni) towards three industrially relevant toxic and hazardous gases: CO, NO, and H2S, using density functional theory (DFT) calculations. The interaction between the gases and the TM-doped PtS2 monolayer substrates was thoroughly investigated, taking into account various adsorption configurations, charge transfer phenomena, band structures, and state densities. Results indicate that the TM dopants markedly enhances the conductivity and gas adsorption capacity of PtS2 monolayer. Specifically, the TM-doped PtS2 monolayers exhibit strong adsorption properties towards CO, NO, and H2S, with the adsorption process identified as chemisorption. By analyzing the alterations in conductivity subsequent to gas adsorption, we discerned that Ni-PtS2 could potentially serve as an effective sensor for CO, NO, and H2S. Consequently, our results furnish a solid theoretical foundation for the development of PtS2-based sensors aimed at detecting these gases. Furthermore, the findings of this research offer valuable insights into the design of gas nanosensors.

Determination of Tioconazole via Spectrophotometry Using Charge Transfer Complex Formation

Determination of Tioconazole via Spectrophotometry Using Charge Transfer Complex Formation

Chromium in Visible‐Light Photocatalysis: Unique Reactivity, Mechanisms and Future Directions

Visible‐light photocatalysis has emerged as a prominent research area in modern organic synthesis and environmental science. As an important transition metal, chromium has garnered widespread attention in the field of visible‐light photocatalysis in recent years, primarily manifested in the following aspects: a) the unique photochemical properties of chromium(III) complexes endow them with longer excited‐state lifetimes and higher reactivities; b) by harnessing visible light to induce single‐electron transfer or hydrogen atom transfer to generate radicals, which subsequently form alkyl‐chromium(III) intermediates with chromium(II) ligands, these intermediates can selectively attack electron‐deficient carbonyl compounds, enabling the construction of target products; c) following metals like cerium, copper, iron, nickel, cobalt, titanium, and bismuth, the ligand‐to‐metal charge transfer (LMCT) reaction pathways in chromium photocatalysis have also been extensively investigated.This review will provide a comprehensive summary of recent research on chromium‐mediated photocatalytic reactions, offering an in‐depth exploration of their unique reactivity, mechanisms, and future directions.

Boron-bridged bis(tetrathiafulvalene) zwitterionic neutral radical conductors: substituent effects on intramolecular and intermolecular electronic interactions and physical properties

Abstract We have recently proposed a new molecular design for neutral radical molecular conductors, based on the chemical composition of D2X-type charge-transfer salts (D = π-electron donor molecule, X = monovalent anion). Namely, we connected two tetrathiafulvalene (TTF)-based π-electron skeletons having a charge of +0.5 via a boron anion B–, to obtain a purely organic zwitterionic neutral radical {[(PDT-TTF-Cat)2]+B–}• that shows unique electronic states and properties in the crystal due to the intramolecular and intermolecular interactions of the +0.5-charged π-skeletons. In order to further explore the structural and electronic features of this kind of zwitterionic neutral radical conductor, in this study, we have examined chemical modifications to {[(PDT-TTF-Cat)2]+B–}•. As a result, an analog molecule {[(BMT-TTF-Cat)2]+B–}•, in which propylenedithio (PDT) groups on the TTF terminals in {[(PDT-TTF-Cat)2]+B–}• are replaced by bis(methylthio) ones, was successfully synthesized as air-stable single crystals. Interestingly, this chemical modification causes intramolecular charge disproportionation between the two TTF-based π-skeletons (i.e. the monovalent cation radical TTF+• and the neutral TTF0) coupled to the modulation of the intermolecular distances and interactions between these π-skeletons, leading to electrical and magnetic properties significantly different from those of the crystal of {[(PDT-TTF-Cat)2]+B–}•.

Development of a Highly Sensitive and Stretchable Charge-Transfer Fiber Strain Sensor for Wearable Applications.

Wearable electronics have significantly advanced the development of highly stretchable strain sensors, which are essential for applications such as health monitoring, human-machine interfaces, and energy harvesting. Fiber-based sensors and polymeric materials are promising due to their flexibility and tunable properties, although balancing sensitivity and stretchability remains a challenge. This study introduces a novel composite strain sensor that combines poly(3-hexylthiophene) and tetrafluoro-tetracyanoquinodimethane to form a charge-transfer complex (CTC) with carbon nanotubes (CNTs) on a styrene-butadiene-styrene substrate. The CTC improves conductivity through effective charge transfer, while CNTs provide mechanical reinforcement and maintain conductive paths, preventing cracks under large strains. Purposefully introduced wrinkles in the structure enhance the detection of small strains. The sensor demonstrated a broad strain-sensing range from 0.01 to 200%, exhibiting high sensitivity to both minor and major deformations. Mechanical tests confirmed strong stress-strain performance, and electrical tests indicated significant conductivity improvements with CNT integration. These results highlight the potential of the sensor for applications in health monitoring, human-machine interfaces, and energy harvesting, effectively mimicking the tactile sensing abilities of human skin.

Design and synthesis of heterocycle-based push-pull NLOphores: A comprehensive study of their linear and non-linear optical properties

Push-pull chromophores, with strong intramolecular charge transfer (ICT), exhibit high ground-state polarization, driving strong NLO responses. The donor and acceptor abilities of the groups in the investigated compounds influence ICT, so the nonlinear response of these compounds was analyzed in relation to their strength. Two different families of NLOphores were synthesized through [2 + 2] cycloaddition-retroelectrocyclizations of heterocycle-based electron-rich alkynes with tetracyanoethylene (TCNE) and tetracyanoquinodimethane (TCNQ). The λmax values of push-pull chromophores, particularly for charge transfer bands, fall within the range of 424–758 nm. The linear and nonlinear optical properties of these NLOphores were subsequently examined through a combination of experimental and theoretical methods. NLO measurements were conducted using a validated custom-made Z-scan device. The nonlinear absorption coefficients range from −1.44 × 10−4 cm.W−1 to −9.90 × 10−4 cm.W−1, while nonlinear refractive indices range from −1.59 × 10−7 cm2. W−1 to −2.26 × 10−6 cm2. W−1. As expected from their molecular structures, the TCNQ products displayed stronger nonlinear responses than the TCNE products.

Nickel oxide nanoparticles embedded in polymer-matrix nanocomposite prepared by nanosecond laser ablation method for optoelectronic applications

The polymeric PVA structure embedded with nickel oxide nanoparticles (NiO NPs) was synthesized using nanosecond pulsed laser ablation in liquid media technique for optoelectronic applications. A comprehensive investigation was conducted on the optical and electrical characteristics of the fabricated films to demonstrate the proficiency of the proposed nanocomposite film in that particular domain. Different weights of NiO nanoparticles were generated by embedding them in PVA film using different ablation durations. It was shown that as the concentration of NiO embedded in PVA increased in correlation with the ablation period, the absorption peak changed to a longer wavelength, and the absorption edge of PVA changed towards lower photon energy with a reduction in the band gap density. Followed by the increase in disorder degree through the addition of NiO NPs, while an average value of the dispersion energy is identical, and the nonlinear parameters (χ(3) and n2) increase. Also, the results emphsies that the dielectric characteristics were affected as the concentration of NiO NPs increased due to the rise in the density of states, which resulted in the generation of polarization. Due to the creation of the charge transfer complex, the optical conductivity of the produced nanocomposites rises as the concentration of NiO NPs increases. Therefore, the optical and electrical characteristics of PVA are significantly affected by the incorporation of NiO nanocomposites.

Selective Photocatalytic Oxidation of 5‐Hydroxymethylfurfural using Ce doped TiO2: A Crucial Role of Defective Sites

AbstractTransforming platform compounds with conventional catalysts, such as homogeneous and heterogeneous, into valuable chemicals encounters challenges associated with entailing high temperature/pressure and reusability during the reaction. To address these challenges, photocatalysis is one of the promising approaches, especially with visible‐light‐driven photocatalysts for selective transformation. A series of cerium‐doped TiO2 (CexTiO2; x=0.5, 1, 3 and 5 wt %) are prepared via a simple coprecipitation method for the cocatalyst‐free selective oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐diformylfuran (DFF) under visible light illumination. Introducing Ce into the network to TiO2 generates impurity energy levels, reduces the band gap, and extends the spectral response range. This also causes slight distortion to the surface structure, thereby originating defective sites and various surface oxygen species, confirmed by X‐ray photoelectron spectroscopy and electron paramagnetic resonance studies. The HMF adsorption studies infer that HMF forms a surface complex with CeTiO2, facilitating the formation of ligand‐to‐metal charge transfer complex (LMCT) under visible light (~420 nm), which efficiently catalyzes the conversion of HMF (54.4 %) to DFF with a selectivity of >99 %. In‐situ DRIFTS and surface passivation studies provide insight into the interaction between HMF and surface acidic/basic sites along with hydroxyl groups of CeTiO2, which subsequently convert selectively to DFF.

Mer-M(CO)3(PNP)0/+ pincer complexes (M = W(0) or Re(I); PNP = 4,5-bis(diphenylphosphino)acridine): synthesis, spectroscopy and anti-Kasha emission.

Two isoelectronic and isostructural W(0) and Re(I) complexes mer-W(CO)3(PNP) (1) and [mer-Re(CO)3(PNP)]Cl (2) (PNP = 4,5-bis(diphenylphosphino)acridine) were synthesized and characterized by X-ray diffraction, infrared, electronic absorption and emission spectroscopy, and cyclic voltammetry. Structures of these complexes show a metal center bonded to the pincer ligand and two axial CO and one equatorial CO ligands. DFT calculations showed that the LUMOs of both complexes are the lowest energy π* orbitals localized in the acridine part of the ligand. The HOMO of 1 is dominated by the dπ orbital of W(0) while the HOMO of 2 has a substantial contribution from the highest energy π orbital of the acridine ring. TD-DFT calculations were performed to assist assignment of the UV-vis absorption spectra. The UV-vis absorption spectrum of 1 shows a very low energy W → π* (acridine) metal-to-ligand-charge-transfer (MLCT) absorption band that ranges from visible (500 nm) to near-infrared (>900 nm) regions and an intense acridine π → π* absorption band at 410 nm. There is a blue-green window in the ∼450-500 nm range between the π → π* and W → π*(acridine) MLCT absorptions. The absorption spectrum of 2, dominated by intense π → π* absorptions, shows no distinct low energy MLCT band. Complex 1 is luminescent, displaying acridine-based ππ* fluorescence at 501 nm which is anti-Kasha as it is higher in energy than the lowest energy excited state.

Parallel Plate Capacitor Model at the Nanoscale for Stable and Gigantic SERS Activity of the 4-MBA@R-AuNP-4-MBA@R-AuNP System.

Selective use of ingredients out of a specific natural product (e.g., fruit, leaf, flower, or honey extract) or their mixture (e.g., bacteria, viruses, fungi, plants, etc.) by smart manipulation of precursors and reaction conditions to synthesize nanoparticles can provide us a low-cost, environmentally friendly route for their industrial-scale production. The presence of more than one active ligand (sourced natural product extract) on the surface not only makes them the most stable (electrostatically) and monodispersed (controlled kinetics) but also devoid of any external ligand-assisted aggregation. This empowered us to modify the surface of the nanoparticles in a monolayered fashion or to couple between nanoparticles through a ligand-assisted chemical coupling pathway to avoid their aggregation and hence to keep their nanoscale property intact. A metal-to-ligand charge transfer (MLCT) trajectory combined with electromagnetic field-induced coherent capacitive coupling between two nanoparticles was introduced to explain the gigantic Raman enhancement observed from these nanoparticles. As a model system, we have synthesized the nanoparticles from rose extract as the active ligand ingredient source for 2-phenyl ethanol, linalool, citronellol, nerol, geraniol, pyrogallol (C6H3(OH)3), and quercetin (3,3',4',5,7-pentahydroxyflavone) and the surface of the synthesized nanoparticles has been modified by 4-mercaptobenzoic acid (4-MBA) acting as a Raman tag. The obtained structural and spectroscopic data correlate well between our numerical and density functional theory (DFT)-based calculations to justify their gigantic SERS activity, which may lead us to propose an unexplored coherent capacitive coupling-based Raman enhancement mechanism.

Tuning Electron Transfer Coupling and Exchange Interaction in Bis-triarylamine Radical Cations and Dications by Bridge Electron Density.

The influence of the electron density of a bridge connecting two redox centers on both the intervalence hole transfer and the magnetic superexchange was investigated in a series of bridged bis-triarylamine mono- and dications. In this series, the bridge was 2,7-fluorenyl, where the bridge electron density was modified by substituents at the 9-position. For the mixed-valence monocations, the observation of both an intervalence charge transfer (IVCT) band and an absorption band associated with an electron transfer from the bridging fluorene to the triarylamine radical cation centers allowed determination of the electron transfer couplings in the framework of the three-state generalized Mulliken-Hush theory. Comparison of the derived couplings with those obtained from a classical two-state approach demonstrates an enhancement of the electronic coupling which increases with decreasing bridge state energy. For the dicationic diradical counterparts, the singlet-triplet gap (exchange interaction) was determined both experimentally and by quantum chemical methods. Hereby, an increase of antiferromagnetic coupling with a lowering of the bridge state energy by electron donating substituents was observed. Analysis of the involved molecular orbitals suggests that the ferromagnetic coupling is inversely proportional to the square of the bridge energy, which is also supported by the experimental findings. This influence of the bridge state energy on both types of interactions, electron transfer and magnetic exchange, provides a design guideline for fine-tuning the properties of electronically coupled organic redox dyads by variation of the bridge electron density.

Automated ECL Aptasensing Platform from an Intrarticular Radical Annihilation Route for Distinguishing Glioma Stages.

Nowadays, continuous efforts have been devoted to designing stable and high-efficiency electrochemiluminescence (ECL) emitters as alternatives for tris(2,2'-bipyridine)-ruthenium(II) (Ru(bpy)32+) in medical research. Herein, a novel ECL emitter was obtained by coordinating crystalline covalent triazinyl frameworks (cCTFs) with Ru2+ (termed Ru-cCTFs), which exhibited strong ECL emission by the ligand to metal charge transfer (LMCT) route. After its integration with 4-mercaptopyridine (SH-Py), the resultant SH-Py-Ru-cCTFs achieved 2.3-fold enhancement in the ECL efficiency by employing Ru(bpy)32+ as a standard, which involved a dynamic "intrarticular radical annihilation" ECL pathway. On such foundation, an automated ECL (A-ECL) aptasensor was constructed with an "on-off-on" model and magnetic separation upon linkage of the SH-Py-Ru-cCTFs with streptavidin (SA) magnetic beads (MBs). This automatic assay of miRNA-182 showed a wider linear range from 1.0 to 100.0 fM with a correlation coefficient (R2) of 0.994, a lower limit of detection (LOD) down to 0.28 fM, and faster operation within 41 min. Impressively, this bioassay facilely distinguished the stages of glioma disease from clinical blood samples with high accuracy. Hence, this research sheds light on how to develop advanced ECL luminophores and an automatic method, showing substantial insights into pathogenesis research of gliomas.

Temperature-dependent generalized ellipsometry of the metal–insulator phase transition in low-symmetry charge-transfer salts

Determining the optical and electronic properties of strongly anisotropic materials with symmetries below orthorhombic remains challenging; generalized ellipsometry is a powerful technique in this regard. Here, we employ Mueller matrix spectroscopic and temperature-dependent ellipsometry to determine the frequency dependence of six components of the dielectric-function tensor of the two-dimensional charge-transfer salt α-(BEDT-TTF)2I3 across its metal–insulator transition. Our results offer valuable insights into temperature-dependent changes of the components of the spectroscopic dielectric-function tensor across the metal–insulator transition. This advanced method allows extension to other electronic transitions.

Functionalized MBene, Ti[formula omitted]BX[formula omitted] (X=Si, Ge, P, As) as potential excellent anode materials for lithium and sodium-ion batteries: A first-principles study

In the search for next-generation energy storage devices, superior-performance alternative electrode materials based on two-dimensional materials for rechargeable metal-ion batteries are essential. Here, we explored group III and IV functionalization of 2D Ti2B, Ti2BX2 (X=Si, Ge, P, As) as anode materials for Li and Na ion batteries using first-principles calculations. The structures had excellent metallic properties and demonstrated energetically favorable adsorptions for metal ions. Analyzing charge transfer and electronic band structures, silicon and phosphorous-functionalized Ti2B (Ti2BSi2 and Ti2BP2) showed the most potential. The energy band diagrams showed that both Ti2BSi2 and Ti2BP2 had metallic characteristics after Li and Na-ion adsorption, which offered considerable advantage for rechargeable-ion batteries. The structures exhibited low energy barriers for Li and Na-ion migration. The minimum energy barriers calculated for Na were 0.08 eV for Ti2BSi2 and 0.24 eV for Ti2BP2. Theoretical specific capacity and open circuit voltage were calculated using maximum layer adsorption. For both Li and Na, high values of specific capacity and low values of open circuit voltage (¡ 1 V) were found. Ti2BSi2 had the best performance, with a theoretical specific capacity of 1647.10 and 1317.68 mA h/g for Li and Na, respectively. Its open circuit voltages for Li and Na were 0.65 and 0.38 V. The insights of this study will be beneficial in fabricating high-performing Ti2BX2-based anodes for rechargeable Li and Na ion batteries.

Advances of the Holographic Technique to Test the Basic Properties of the Thin-Film Organics: Refractivity Change and Novel Mechanism of the Nonlinear Attenuation Prediction.

A large number of the thin-film organic structures (polyimides, 2-cyclooctylarnino-5-nitropyridine, N-(4-nitrophenyl)-(L)-prolinol, 2-(n-Prolinol)-5-nitropyridine) sensitized with the different types of the nano-objects (fullerenes, carbon nanotubes, quantum dots, shungites, reduced graphene oxides) are presented, which are studied using the holographic technique under the Raman-Nath diffraction conditions. Pulsed laser irradiation testing of these materials predicts a dramatic increase of the laser-induced refractive index, which is in several orders of the magnitude greater compared to pure materials. The estimated nonlinear refraction coefficients and the cubic nonlinearities for the materials studied are close to or larger than those known for volumetric inorganic crystals. The role of the intermolecular charge transfer complex formation is considered as the essential in the refractivity increase in nano-objects-doped organics. As a new idea, the shift of charge from the intramolecular donor fragment to the intermolecular acceptors can be proposed as the development of Janus particles. The energy losses via diffraction are considered as an additional mechanism to explain the nonlinear attenuation of the laser beam.

Ligand-to-Metal Charge Transfer (LMCT) Catalysis: Harnessing Simple Cerium Catalysts for Selective Functionalization of Inert C-H and C-C Bonds.

ConspectusChemists have long pursued harnessing light energy and photoexcitation processes for synthetic transformations. Ligand-to-metal charge transfer (LMCT) in high-valent metal complexes often triggers bond homolysis, generating oxidized ligand-centered radicals and reduced metal centers. While photoinduced oxidative activations can be enabled, this process, typically seen as photochemical decomposition, remains underexplored in catalytic applications. To mitigate decomposition during LMCT excitation, we developed a catalytic cycle integrating in situ coordination, LMCT, and ligand homolysis to activate ligated alcohols transiently into alkoxy radicals. This catalytic approach leverages Ce(IV) LMCT excitation and highly reactive alkoxy radical intermediates for selective functionalizations of C(sp3)-H and C(sp3)-C(sp3) bonds under mild conditions. In this Account, we discuss these advancements, highlighting the practical utility of cost-effective cerium salts as catalysts and their potential to develop innovative transformations, addressing long-standing synthetic challenges.Selective functionalization of chemically inert C(sp3)-H bonds has long posed a significant challenge. We first detail our research using LMCT-enabled alkoxy radical-mediated hydrogen atom transfer (HAT) processes for selective C(sp3)-H functionalizations. Using readily available CeCl3, we established a general protocol for employing free alcohols in the Barton reaction. By integrating LMCT and HAT catalysis, we introduced a selective photocatalytic strategy for functionalizing feedstock alkanes, converting gaseous hydrocarbons into valuable products. Employing simple cerium salts like Ce(OTf)3 and CeCl3, we achieved selective C-H amination of methane and ethane at ambient temperature, achieving turnover numbers of 2900 and 9700, respectively. This catalytic manifold has been further exploited to address the site-selectivity challenge in the C-H functionalization of linear alkanes. The use of methanol as a cocatalyst enabled preferential functionalization of the most electron-rich sites, achieving a high intrinsic selectivity over 12:1 of secondary vs primary sites in pentane and hexane.Next, we discuss the catalytic utilization of alkoxy-radical-mediated β-scission, a frequently encountered side reaction in HAT transformations, for selective cleavage and functionalization of C-C bonds. The versatility of the LMCT catalytic platform facilitates the generation of alkoxy radicals from various free alcohols. In our initial demonstration of LMCT-enabled C(sp3)-C(sp3) bond activation, we developed a cerium-catalyzed ring-opening and amination of cycloalkanols, providing an effective protocol for cleaving unstrained C-C bonds. This strategy has been successfully applied to various radical cross-coupling processes, leading to innovative transformations such as ring expansions of cycloalkanols, dehydroxymethylative alkylation, amination, alkenylation, and ring expansions of cyclic ketones. These results highlight the synthetic potential of employing LMCT-mediated β-scission and ubiquitous C-C bonds as unconventional functional handles for generating molecular complexity.Lastly, we delve into our mechanistic investigations. Beyond the catalytic application of Ce(IV) LMCT in various transformations, we have undertaken comprehensive mechanistic studies. These investigations encompass characterization of Ce(IV) alkoxide complexes to elucidate their structures, evaluation of their photoactivity and selectivity in radical generation, and elucidation of kinetic pathways associated with transient LMCT excited states. Our research has revealed ultrafast bond homolysis, back electron transfer, and the selectivity of heteroleptic complexes in homolysis, providing crucial insights for advancing LMCT catalysis.

Enabling Visible Light Sensitization of YbIII, NdIII and ErIII in Dimeric LnIII/GaIII Metallacrowns through Functionalization with RuII Complexes for NIR-II Multiplex Imaging.

Multiplex imaging in the second near-infrared window (NIR-II, 1000-1700 nm) provides exciting opportunities for more precise understanding of biological processes and more accurate diagnosis of diseases by enabling real-time acquisition of images with improved contrast and spatial resolution in deeper tissues. Today, the number of imaging agents suitable for this modality remains very scarce. In this work, we have synthesized and fully characterized, including theoretical calculations, a series of dimeric LnIII/GaIII metallacrowns bearing RuII polypyridyl complexes, LnRu-3 (Ln = YIII, YbIII, NdIII, ErIII). Relaxed structures of YRu-3 in the ground and the excited electronic states have been calculated using dispersion-corrected density functional theory methods. Detailed photophysical studies of LnRu-3 have demonstrated that characteristic emission signals of YbIII, NdIII and ErIII in the NIR-II range can be sensitized upon excitation in the visible range through RuII-centered metal-to-ligand charge transfer (MLCT) states. We have also showed that these NIR-II signals are unambiguously detected in an imaging experiment using capillaries and biological tissue-mimicking phantoms. This work opens unprecedented perspectives for NIR-II multiplex imaging using LnIII-based molecular compounds.

Band-gap engineering enabled emission switch in solid-solution phosphors LiIn1-xScxGeO4:Bi3+ for spectral-temporal anti-counterfeiting

The interaction between matrix lattice and doped activator has long been pivotal topic in the research of the state-of-the-art functional materials, particularly luminescent materials. With the ceaseless development of advanced anti-counterfeiting, there are imperative need for developing luminescent materials with wide emission tunability, excellent visibility, and adjustable persistent luminescence. Herein, we present a paradigm to obtain great emission tunability in a solid-solution phosphors LiIn1-xScxGeO4:Bi3+ (x = 0–1) via band-gap engineering. With the increase in Sc content, the band-gap enlarges, causing the Bi3+ emissions gradually shift from 580 to 456 nm. As Sc substitution continues, the Bi3+ emissions transfer from the metal-to-metal charge transfer band to the inter s-p transition, resulting in a rapid shift in emission from 456 to 356 nm. This emission shift not only achieves a record total tunability of 224 nm among Bi3+-doped solid-solution phosphors but also an informative band-gap dependent emission mechanism of the Bi3+ activator. Furthermore, the samples gradually exhibited a persistent luminescence through the substitution process, attributed to the increasing traps by the thermoluminescence analysis. Leveraging these unique spectral properties, we designed two types of patterns that can be distinguished from color and time within the visible light range, demonstrating that the obtained phosphors can serve as promising candidate materials for spectral-temporal anti-counterfeiting.