Luminescence Properties Research Articles

Two-Coordinate Dinuclear Donor-Gold(I)-Acceptor Complexes Exhibiting Multiple Excitation Wavelength Dependent Phosphorescence.

Two-coordinate Au(I) complexes with a donor-metal-acceptor (D-M-A) structure have shown rich luminescent properties. However, charge-neutral dinuclear donor-metal-acceptor type Au(I) complexes featuring aurophilic interactions have been seldom explored. Herein, we describe the structures and photoluminescence properties of two dinuclear Au(I) complexes, namely DiAu-Ph and DiAu-Me. Single crystal X-ray structural analysis of DiAu-Ph reveals a short intramolecular Au-Au distance of 3.224 Å. In dilute solution and doped films, excitation wavelength dependent multiple phosphorescence phenomena were observed for these dinuclear complexes. Theoretical calculations reveal that the aurophilic interaction causes increased contribution of the Au d orbital to the highest occupied molecular orbitals. Thus, the gap between singlet and triplet excited states (ΔEST) is enlarged, which disables the thermally activated delayed fluorescence (TADF). Moreover, the large energy separation (0.45-0.52 eV) and the different orbital configurations between the various excited states result in an inefficient internal conversion, accounting for their multiple phosphorescence properties.

Unlocking multi-photon excited luminescence in pyrazolate trinuclear gold clusters for dynamic cell imaging

The family of coinage-metal-based cyclic trinuclear complexes exhibits abundant photophysical properties, promising for diverse applications. However, their utility in biochemistry is often hindered by large particle size and strong hydrophobicity. Meanwhile, the investigation into multi-photon excited luminescence within this family remained undocumented, limiting their potential in bio-imaging. Herein, we unveil the multi-photon excited luminescent properties of pyrazolate-based trinuclear gold(I) clusters, facilitated by excimeric gold(I)···gold(I) interactions, revealing a nonlinear optical phenomenon within this family. Furthermore, to address issues of poor biocompatibility, we employ electrospinning coupled with hydroxypropyl-beta-cyclodextrin as the matrix to fabricate a flexible, durable, transparent, and red emissive film with a photoluminescence quantum yield as high as 88.3%. This strategy not only produces the film with sufficient hydrophilicity and stability, but also achieves the downsizing of trinuclear gold(I) clusters from microscale to nanoscale. Following the instantaneous dissolution of the film in the media, the released trinuclear gold(I) nanoparticles have illuminated cells and bacteria through a real-time, non-toxic, multi-photon bio-imaging approach. This achievement offers a fresh approach for utilizing coinage-metal-based cyclic trinuclear complexes in biochemical fields.

Substituent effect induced circularly polarized luminescence enhancement of Eu(III) enantiomers

Circularly polarized luminescence (CPL) has received much attention in optical displays, information storage, and biological probes. Designing effective strategy to improve the CPL activities is significant for complex materials. Structural modification is a rational way which is seldom reported. In this work, three chiral binuclear Eu(III) complexes coordinated with different chiral Schiff base ligands were designed and synthesized. CPL performances of these Eu(III) complexes were substantially improved by polarity of substituents at the chiral carbon sites of the ligands, leading to a five-fold increase in the luminescence dissymmetry factor (glum). Additionally, three complexes exhibited similar luminescence properties with the characteristic peaks of Eu(III) ion, which can be rapidly quenched by Co(II) ion, allowing their further applications in anti-counterfeiting and sensors. Therefore, this work not only uncovers the relationship between the substituents of chiral ligand and the corresponding CPL properties of Eu(III) complexes to some extent, but also creates opportunities for design and synthesis of Eu(III) complexes with excellent CPL activity.

Low-temperature synthesis and luminescence properties of blue-emitting β-SiAlON:Eu2+ phosphor using melamine as a self-propagating raw material

Sialons are widely recognized for their rigid lattice structure, high visible light transmittance, and excellent thermal stability, making them suitable matrix materials for activators. In this paper, we successfully prepared β-sialon phosphors, β-Si6-zAlzOzN8-z:Eu2+ (β-SiAlON:Eu2+), using an organic precursor method at a low synthesis temperature for the first time. X-ray diffraction analysis and Rietveld refinement confirm the β-SiAlON:Eu2+ phosphor possesses a hexagonal structure with a P63 space group. Under 320 nm excitation, β-SiAlON:Eu2+ phosphor exhibits a blue emission band centered at 415 nm due to the 5d → 4 f electron transition of Eu2+, which differs significantly from other β-SiAlON:Eu2+ phosphors with green emission. It is interesting that excessive Eu2+ activators make β-SiAlON:Eu2+ phosphor possess a green emission band centered at 510 nm. Therefore, the light-emitting color of β-SiAlON:Eu2+ phosphor shifts from the blue to the green with the increase of Eu2+ concentration. Furthermore, the activation energy of β-SiAlON:0.02Eu2+ sample is calculated to be about 0.2527 eV, which confirms β-SiAlON:Eu2+ phosphor has good thermal stability. The article presents a low-temperature and cost-effective synthesis method for preparing sialons, as well as a novel blue β-SiAlON phosphor for solid-state lighting.

One pot synthesis and crystal of N-benzoyl(benzo)thiazol-2-amine borodifluoride complexes (NBO) with aggregation induced luminescence properties

In this paper, N-benzoyl(benzo)thiazol-2-amine borodifluoride complexes (NBOs) were synthesized directly from benzoyl chloride and (benzo)thiazol-2-amine by one-pot method. The molecular structures of the target compounds were characterized by nuclear magnetic resonance (NMR), high resolution mass spectrometry and single crystal X-ray diffraction. The optical properties of the compounds were measured by UV–Vis absorption and fluorescence spectra. In CH2Cl2, this compounds exhibit large Stokes shifts, the maximum absorption peaks of NBO-1, NBO-2 and NBO-3 are 327 nm, 342 nm and 362 nm, and the maximum emission peaks are 400 nm, 442 nm and 498 nm, respectively. It can also be found that the absorption and emission spectra are redshifted with the increase of the conjugated system. Further more, we found that NBO-2 and NBO-3 molecules with additional benzo structure have the properties of aggregation induced emission, while NBO-1 show weak fluorescence in both solution and aggregation state.

Influence of Pr3+ co-doping on the luminescent properties of CGA:2 at.% Ho single crystal fibers

Ho3+, Pr3+ co-doped CaGdAlO4 (Ho,Pr:CGA) crystal fibers were successfully grown by the micro-pulling-down (μ-PD) technique for the first time. Detailed investigations were conducted on the polarized absorption spectra, fluorescence spectra, and lifetime decay curves. The 2 at.% Ho, 0.4 at.% Pr:CGA crystal fiber exhibits a broad absorption band at 1147 nm with full width at half maximum (FWHM) of 25.5 nm and 64.5 nm for σ and π polarization, respectively. Increasing the concentration of Pr3+ led to a decrease in emission intensity at 2001 nm and an increase in emission intensity at 2861 nm. The FWHMs of the crystal fiber containing 2 at.% Ho and 0.4 at.% Pr:CGA at 2861 nm were 44.5 nm for σ polarization and 24.3 nm for π polarization. Additionally, the lifetime ratio (5I7/5I6) decreases from 25.18 to 2.85 in the crystal fibers containing 2 at.% Ho:CGA and 2 at.% Ho, 0.4 at.% Pr:CGA, respectively. These findings suggest that the presence of deactivated Pr3+ ions can significantly reduce the lifetime gap between the 5I6 and 5I7 energy levels, potentially mitigating the self-termination phenomenon on the ∼3 μm emission.

Reversible mechanochromic luminescence in a binuclear zero-dimensional Cd(II) complex through transformation between exciplex and excimer

In this work, the mechanochromic luminescence (MCL) property of a binuclear zero-dimensional cadmium complex with a variety of weak interactions is investigated. It exhibits a reversible transition between blue (445 nm) and yellow-green (470 nm) emission under the alternating treatments of grinding and CH3CN fumigation. The mechanism of MCL is proposed by combining the structural features, characterization results and theoretical calculations. During the grinding process, the ordered stacking of the structural units is disrupted and the crystalline state is transformed into an amorphous state, which is accompanied by a transition of the luminescent center from exciplex to excimer. In addition to exploring the MCL properties of a binuclear cadmium complex, this work provides feasible ideas for studying the response mechanism.

Theoretical investigation of the excited-state intramolecular double proton transfer process of 2,2'-(benzo[1,2-d:4,5-d']bis(thiazole)-2,6-diyl)diphenol.

In this work, the excited state intramolecular double proton transfer (ESIDPT) mechanism of 2,2'-(benzo[1,2-d:4,5-d']bis(thiazole)-2,6-diyl)diphenol (BTAP) is proposed using density functional theory (DFT) and time-dependent DFT (TDDFT). The changes in bond lengths, bond angles and IR vibrational spectra associated with two intramolecular hydrogen bonds of BTAP upon photoexcitation indicate that the hydrogen bonds are strengthened in the excited state, facilitating the ESIDPT process. Investigation of the constructed S1-state potential energy surface proposes that BTAP prefers a stepwise ESIDPT mechanism. Electronic spectra and frontier molecular orbitals (FMOs) are also presented to illustrate the luminescent properties of BTAP.

Highly efficient and water-resistant BaGa4S7:Eu2+ phosphor prepared by a self-reduction method

The development of eco-friendly luminescent materials is imperative for the advancement of phosphor-based technologies. This study corroborates the self-reduction of Eu3+ to Eu2+ through analyses utilizing photoluminescence (PL), excitation spectroscopy (PLE), and X-ray photoelectron spectroscopy (XPS). Density functional theory (DFT) calculations demonstrate that Eu2+ ions can efficaciously substitute Ba2+ ions within the BaGa4S7 lattice, preserving its structural integrity. Upon blue light excitation, BaGa4S7:Eu2+ manifests a robust green emission attributed to Eu2+ ions, showcasing a peak wavelength near 526 nm. The quantum yield (QY) of BaGa4S7:Eu2+ is remarkably high, registering at 74.8 %. Moreover, the temperature-dependent luminescence properties of BaGa4S7:Eu2+ phosphor were subjected to thorough investigation. Water resistance assays indicate that the sample preserves 76 % of its initial luminous intensity following 40 days of aqueous immersion. Additionally, BaGa4S7:Eu2+ based phosphor-converted white light-emitting diodes (WLEDs) demonstrate emission of high-quality white light. This unique water-resistant green emission sulfide phosphor is expected to have potential applications in lighting fields.

An Overview of Various Applications of Cadmium Carboxylate Coordination Polymers.

This review highlights the most recent applications of Cd(II)-carboxylate-based coordination polymers (Cd(II)-CBCPs), such as sensors, catalysts, and storage materials, in comparison with those of Zn(II) counterparts. A wide range of species with luminescence properties were designed by using proper organic fluorophores, especially a carboxylate bridging ligand combined with an ancillary N-donor species, both with a rigid structure. These characteristics, combined with the arrangement in Cd(II)-CBCPs' structure and the intermolecular interaction, enable the sensing behavior of a plethora of various inorganic and organic pollutants. In addition, the Lewis acid behavior of Cd(II) was investigated either in developing valuable heterogeneous catalysts in acetalization, cyanosilylation, Henry or Strecker reactions, Knoevenagel condensation, or dyes or drug elimination from wastewater through photocatalysis. Furthermore, the pores structure of such derivatives induced the ability of some species to store gases or toxic dyes. Applications such as in herbicides, antibacterials, and electronic devices are also described together with their ability to generate nano-CdO species.

Analysis of luminescent properties of 40PbO–35Bi2O3–25Ga2O3 glasses doped with Er2O3

The Er3+ doped lead–bismuth–gallium oxide glasses were prepared by melt quenching technique. The spectral and luminescent properties were analyzed based on experimental and theoretical calculations. Analysis of Er3+ concentration dependences of density and electronic optical polarizability was carried out. The radiative lifetime values for 4S3/2 and 4F9/2 energy states were calculated using Judd-Ofelt theory. In the glassy system under study, the concentration quenching of state 4S3/2 was discovered at content of erbium ions above 0.869 × 1020 cm−3. It was also shown that 4F9/2 energy state was isolated from concentration effects and showed an increase in luminescence intensity with increasing concentration of activator ions. The luminescence quantum efficiency for transition 4S3/2 → 4I15/2 was about 40%, which allows us to consider this system as a glassy matrix effective for activation by rare-earth ions.

Substituent effects on the ESIPT process of H2O2 sensing product 1,3-bis(bispyridin-2-ylimino) isoindolin-4-ol: A theoretical study

H2O2 plays an important role in a variety of physiological processes, but its overproduction or accumulation can lead to oxidative damage and related diseases, so it is crucial to establish accurate H2O2 detection methods. Fluorescence sensing as a potential method, the design and modulation of its luminescent properties are crucial to the detection results. In this work, we investigated the sensing mechanism of a novel H2O2 fluorescent probe (P1) and examined the role of substituent effects in modulating the fluorescence properties of its reaction products. The results show that the non-fluorescence property of the probe is due to twisted intramolecular charge transfer (TICT) mechanism resulting from a torsion of the excited state molecular conformation, and the fluorescence turn-on upon recognition of H2O2 by the probe is due to the reaction product (BBYI1) following the excited state intramolecular proton transfer (ESIPT) process. When the substituent is an electron-donating group, the energy barrier of the ESIPT reaction is lowered, promoting luminescence, while the electron-withdrawing group has the opposite effect. In summary, the present work may offer a theoretical foundation for the development of more sensitive fluorescent probes for ESIPT-based H2O2 detection.

Nitrogen-Doped Carbon Dots: A New Powerful Fluorescent Dye with Substantial Effect on Bacterial Cell Labeling.

Carbon dots (CDs)-minute carbon nanoparticles with remarkable luminescent properties, photostability, and low toxicity-show potential for various applications. CDs synthesized using citric acid and urea are the least toxic to biological environments. Here, we aimed to explore the effect of CDs synthesized using citric acid and urea at 50, 33, and 25% (CDs 1/1, 1/2, and 1/3, respectively) weight ratios in a microwave on bacterial cell fluorescence sensing and labeling. The nanoscale properties of CDs were investigated via transmission electron microscopy and dynamic light scattering particle size analysis. X-ray powder diffraction confirmed the graphitic structures of CDs. X-ray photoelectron spectroscopy revealed that the nitrogen content increased gradually with increasing urea ratios, indicating functional group changes. Transient photoluminescence decay periods demonstrated superior fluorescence intensity of CDs 1/3 under blue, green, and red lights. The use of CDs was notably more efficient than traditional methods in staining bacterial cells. Fluorescence microscopy of 10 g-positive and 10 g-negative bacteria revealed enhanced staining of Gram-positive strains, with CDs 1/3 presenting the best results. The CDs exhibited excellent photostability, maintaining poststaining fluorescence for 100 min, surpassing the performance of conventional dyes. CDs could serve as potential fluorescent dyes for the rapid discrimination of Gram-positive and Gram-negative bacteria.

Warm red light emitting Eu(III) complexes synthesis and analysis including computational methods for photonic applications

Six luminescent europium organic complexes have been synthesized and studied for their luminescent properties. The synthesized complexes were analyzed through elemental analysis, XRD, SEM, EDAX, FT-IR, NMR and thermogravimetry. The complexes exhibit crystalline behavior and possess decent thermal stability. Photoluminescence study on complexes were conducted in both solid and solution states, the results indicate the characteristic red emission. With the addition of ancillary ligands, water molecules are replaced from inner coordination sphere, leading to enhanced luminescence properties. The colorimetric parameters (CIE, CP%, CCT, u′, v′) suggest aptness of these complexes in red light illuminating OLEDs. The J-O parameters were calculated experimentally and theoretically with the help of LUMPAC software. Theoretical and experimental results agree well reflecting the efficacy of the outcomes. As a result of red emission, these complexes could have interesting photonics applications. The biological studies indicate the probable use of these complexes in the medical industry.

Revelation of room temperature liquid crystallinity and yellow-orange electroluminescence (EQE>7%) in a columnar self-assembled N-annulated perylene bisimide

The synthesis of highly fluorescent compounds is a critical necessity to facilitate cost-effective and metal-independent production of organic light-emitting diodes (OLEDs). This investigation introduces a readily soluble, electron-deficient N-annulated perylene bisimide (PBI-NST) equipped with a swallow tail, exhibiting room temperature columnar oblique mesophase with a low clearing point and high photoluminescence quantum yield, positioning it as a promising candidate for efficient OLEDs. Leveraging the luminescent properties of PBI-NST, a series of OLED devices were fabricated with PBI-NST as the sole emitter and at various concentrations in CBP host material. Impressively, doped devices employing the compound at 0.5 wt% emitter within the host material CBP displayed an exceptional external quantum efficiency (EQE) of 7.2 %, accompanied by a luminance of 2689 cd/m2. Further, a voltage dependent emission tuning was also noticed. The notable increase in EQE is mainly attributed to the contributions of hybrid local and charge transfer (HLCT) and triplet–triplet annihilation (TTA) process. The substantial enhancement in EQE marks a significant advancement in the application of multifunctional columnar self-assembled materials for OLED development.

Fluorescent Mn3O4 quantum dot as catechol oxidase nanozyme: A robust nano-platform for sensitive dopamine detection

The development of multifunctional semi-conductor nano-enzymes has attained significant interest recently, due to their ease in fabrication, cost-effectiveness, and wide range of applications. In this work, we report the synthesis of ammine-functionalized Mn3O4 quantum dots (Mn3O4 QDs) with excellent luminescence properties. These QDs have been developed via the reduction of permanganate using L-cysteine through a simple, facile one-step bottom-up approach. The steady-state enzyme kinetic studies revealed the superior Catechol-Oxidase mimic activity of the Mn3O4 QDs with a Michaelis-Menten constant (Km) of 133.19 µM, and maximum reaction velocity (Vmax) of 69.40 µMs−1. Due to this superior enzymatic activity, dopamine (DA) gets easily oxidized into DA-quinone and eventually polymerized to form polydopamine. Schiff base/Michael addition reaction between nucleophilic ammine on the surface of QDs and the aromatic chain makes the probe and analyte come closer and leads to the formation of a charge transfer complex, resulting in fluorescence quenching of QDs. This fluorescence quenching has been quantified to develop a turn-off sensor for DA. The sensing characteristics are highly selective and sensitive towards DA with a detection limit of 18 nM. The synthesised Mn3O4 QDs with superior enzyme-mimicking properties have tremendous potential as fluorescent probes in imaging and health care applications.

Synthesis and luminescence properties of carbon quantum dots with core@shell structures

The luminescence stability of carbon quantum dots (CQDs) in air impedes their extensive applications. Ample –NH2 groups on the surface of a green carbon quantum dots (GCQDs) had high organic reactivity, the surface of GCQDs was modified with allyl functional groups through a simple surface substitution reaction (named as GCQD-A). The surface of the GCQD-A was continuously formed a thin organic shell by free radical copolymerization reaction with methyl methacrylate and styrene respectively, and they were named as GCQD@PMMA and GCQD@PS respectively. The allyl functional groups on the surface of GCQD-A, the shell composition of GCQD@PMMA and GCQD@PS were characterized by their 1H nuclear magnetic resonance (1H NMR) data and infrared adsorption spectra. The luminescence stabilities for GCQD@PMMA and GCQD@PS in air were greatly improved compared with that for the GCQDs. The work can provide a novel method to get stable luminescence of CQDs in air, and it will extend their application areas in solid state.

Reversible Local Protonation‐Deprotonation: Tuning Stimuli‐Responsive Circularly Polarized Luminescence in Chiral Hybrid Zinc Halides for Anti‐Counterfeiting and Encryption

Precise control over the organic composition is crucial for tailoring the distinctive structures and properties of hybrid metal halides. However, this approach is seldom utilized to develop materials that exhibit stimuli‐responsive circularly polarized luminescence (CPL). Herein, we present the synthesis and characterization of enantiomeric hybrid zinc bromides: biprotonated ((R/S)‐C12H16N2)ZnBr4 ((R/S‐LH2)ZnBr4) and monoprotonated ((R/S)‐C12H15N2)2ZnBr4 ((R/S‐LH1)2ZnBr4), derived from the chiral organic amine (R/S)‐2,3,4,9‐Tetrahydro‐1H‐carbazol‐3‐amine ((R/S)‐C12H14N2). These compounds showcase luminescent properties; the zero‐dimensional biprotonated form emits green light at 505 nm, while the monoprotonated form, with a pseudo‐layered structure, displays red luminescence at 599 and 649 nm. Remarkably, the reversible local protonation‐deprotonation behavior of the organic cations allows for exposure to polar solvents and heating to induce reversible structural and luminescent transformations between the two forms. Theoretical calculations reveal that the lower energy barrier associated with the deprotonation process within the pyrrole ring is responsible for the local protonation‐deprotonation behavior observed. These enantiomorphic hybrid zinc bromides also exhibit switchable circular dichroism (CD) and CPL properties. Furthermore, their chloride counterparts were successfully obtained by adjusting the halogen ions. Importantly, the unique stimuli‐responsive CPL characteristics position these hybrid zinc halides as promising candidates for applications information storage, anti‐counterfeiting, and information encryption.

Theoretical study on the luminescence mechanism of AIEgens based HOFs adsorbing small molecules

The diversity and reversibility of non-covalent interactions give hydrogen-bonded organic frameworks (HOFs) excellent gas adsorption and separation performance. Here we designed and synthesized HOFs based on aggregation-induced emission luminogens (AIEgens) to visualize the adsorption process of HOFs. We focused on the SQ system and its solvated SQ frameworks by different solvent conditions, employing the thermal vibration correlation function rate formalism coupled hybrid quantum mechanics/molecular mechanics protocol, to elucidate the relation between crystal structure and luminescent properties, as well as the specific adsorption ability of porous SQ HOF crystals on acetylene gas. It is found that compare to SQ crystal, the SQ symmetry in cocrystals are improved, and SQ-DCM cocrystal has the best symmetry. The absorption spectra of five SQ-based crystals are close to each other, and their emission spectra blueshifted from 540 nm of SQ, to 509 nm, 508 nm, 507 nm of SQ-EA, SQ-ACN, SQ-DCM, and then to 495 nm of SQ-TOL, consistent with experimental results. The kic of solvated cocrystals are about 1∼2 orders of magnitude smaller than that of non-solvated crystal SQ, resulting in significantly higher Φexp of solvated cocrystals than that of un-solvated one. DCM with small volume and C2v point group is more suitable for SQ crystal channel, indicating that small free region and shape matching are the key factors affecting the reversibility of crystallization of porous frames during solvent transport. Finally, the volume of the adsorbed gas C2H2 which is close to DCM, is more easily adsorbed by SQ framework. Our study offers theoretical insights into the design of porous crystals for gas adsorption and separation applications.

Synthesis, crystal Structure, theoretical calculation and luminescence properties of Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Zn(Ⅱ) quinolinyl benzimidazole complexes with multiple coordination number induced by proton

The innovative ligand H2L, featuring a benzimidazole structure substituted with 8-hydroxyquinoline and equipped with N,O donor sites, underwent successful synthesis and meticulous characterization. Notably, this ligand was exclusively synthesized through catalysis under protonated conditions, accompanied by an in-depth exploration of the catalytic mechanism. Employing single-crystal X-ray diffraction, we acquired and authenticated four distinct asymmetric double-decker sandwich mononuclear transition metal complexes: [Cu(HL)2]·2H2O, [Co(HL)2]·CH3OH, [Ni(HL)2] and [Zn(HL)2]·CH2Cl2. Among these, complex 1 revealed an intriguing five-coordinate Cu(II) center adopting a distorted square pyramidal geometry, whereas the central metal ions in complexes 2–4 exhibited a six-coordinate configuration, characterized by a distorted octahedral geometry. Noteworthy is the observation that the dihedral angles within the crystal structures of complexes 2–4 approached approximately 90° to a significant extent. To delve deeper into the electronic properties and transitions, meticulous DFT and TD-DFT calculations were performed on both the ligand H2L and complexes 1–4. Furthermore, a comprehensive investigation into the luminescence properties of both H2L and its complexes was conducted, revealing a pronounced luminescence quenching effect in the complexes compared to the ligand. Through thorough analysis utilizing Hirshfeld surface examination and IRI analysis, various weak intermolecular interactions within the system were elucidated.