Luminescent Molecules Research Articles

Creation of Excitation-Driven Hypervalent Tin(IV) Compounds For Aggregation-Induced Emission and Application to Thermoresponsive Luminescent Films Below Freezing Point.

Although many researchers have devoted their much effort to establish the strategy for developing a stimuli-responsive molecule and tuning of their properties according to the preprogrammed design, it is still challenging to create desired molecules from the scratch. We recently demonstrated that the molecules with a large structural difference between the theoretically optimized structures in the ground and excited states have a potential to exhibit stimuli-responsive luminescent properties. We defined these molecules as an excitation-driven molecule and have shown that they are a versatile platform for designing stimuli-responsive luminescent molecules. Herein, based on the concept of excitation-driven molecules, we show that the hypervalent tin-fused azomethine (TAm) compounds possessing aggregation-induced emission (AIE) properties can be obtained by simple chemical modification with a methyl group although conventional TAm derivatives are well known to be highly luminescent compounds in solution. Furthermore, by combining the solid-state luminescence property of AIE and the coordination number shifts of the hypervalent tin atom, the thermoresponsive films operating below the freezing point are fabricated with the polymer. In this study, we apply the concept of excitation-driven molecules to the hypervalent compounds and demonstrate to obtain the novel functional materials.

Self‐assembled small molecule spherulites under mild conditions: High solid‐state quantum yield and unique interconnected structural and fluorescent colors

AbstractSpherulites are generally fabricated from cooling polymer melts, while their fabrication under mild conditions or from small molecule materials has been barely reported. Besides, organic luminescent molecules typically suffer from low quantum yields in a solid state. Moreover, preparing material with interconnected and simultaneous changes in structural and fluorescent colors is challenging. Here, we present the first solution‐derived spherulites with unique interconnected structural and fluorescent colors, self‐assembled from stearoylated monosaccharides at room temperature. D‐galactose stearoyl ester self‐assembled into banded spherulites, containing twisted nanoplates and interconnected simultaneously changing structural and fluorescent colors. In comparison, D‐mannose stearoyl ester can only form non‐banded spherulites, which contain oriented nanoplates and uniform structural and fluorescent colors. Such materials revealed a novel negative correlation between fluorescence and birefringence, termed alignment‐promoted quenching propensity. Remarkably, the solid‐state fluorescence quantum yields of galactose and mannose‐derived spherulites are as high as 49 ± 2% and 51 ± 2% respectively, approximately ten times higher than those of unmodified monosaccharides. These quantum yield values are among the highest of reported organic nonconventional fluorophores and even comparable to those of conventional aromatic chromophores. Moreover, these spherulites manifested an unexpected excitation‐dependent multicolor photoluminescence with a broad‐spectrum emission (410−620 nm). They show multiple peaks in the photoluminescent emission spectra and broad fluorescence lifetime distributions, which should be attributed to the clustering of a variety of oxygen‐containing functional groups as emissive moieties.

Photoluminescence color-tuning with polymer-dispersed fluorescent films containing two fluorinated diphenylacetylene-type fluorophores.

The development of organic light-emitting devices has driven demand for new luminescent materials, particularly after the 2001 discovery of aggregation-induced emission. This study focuses on fluorinated diphenylacetylene-based luminescent molecules, revealing that specific molecular modifications can enhance fluorescence and achieve a wide range of photoluminescence colors. A simple and effective luminescence color-tuning method is proposed to investigate the photoluminescence behavior of two-component polymer dispersion films blended with two types of fluorinated diphenylacetylenes, namely blue- and yellow- or red-fluorescent fluorinated diphenylacetylenes. It is confirmed that if blue and green-yellow or yellow fluorophores are blended in appropriate ratios, a binary blend with color coordinates (0.20, 0.32) can be achieved, which approaches the white point of pure white emission. These findings contribute to the development of effective lighting and display devices as new white-light-emitting materials.

Four-Membered Ring-Embedded Cycloarene Enabling Anti-Aromaticity and Ultra-Narrowband Emission.

The synthesis of fully fused π-conjugated cycloarenes embedded with nonbenzenoid aromatics is challenging. In this work, the first example of four-membered ring-embedded cycloarene (MF2) was designed and synthesized in single-crystal form by macrocyclization and ring fusion strategies. For comparison, single bond-linked chiral macrocycle MS2 without two fused four-membered rings and its linear-shaped polycyclic benzenoid monomer L1 were also synthesized. The pronounced anti-aromaticity of four-membered rings significantly adjusts the electronic structures and photophysical properties of cycloarene, resulting in an enhancement of the photoluminescence quantum yield (PLQY) from 10.66 % and 10.74 % for L1 and MS2, respectively, to 54.05 % for MF2, which is the highest PLQY among the reported cycloarenes. Notably, owing to the embedded anti-aromatic four-membered rings that reduce structural displacements, MF2 exhibits an ultra-narrowband emission with a single-digit full-width at half-maximum (FWHM) of only 7 nm (0.038 eV), which sets a new record among all reported organic narrowband luminescent molecules, and represents the first example of ultra-narrowband emission in conventional polycyclic aromatic hydrocarbons (PAHs) devoid of heteroatoms.

Tandem Solid‐Solution Phase Post‐Synthetic Modification of Porous Molecular Crystals for In‐Situ Generation of Fluorophores

AbstractConventional synthetic methods of organic luminescent molecules often involve labor‐intensive solution‐phase organic synthesis, which violate the principles of atom‐economic transformation. Post‐synthetic modification (PSM) offers a promising alternative, allowing direct transformation from one fluorophore to another. Although PSM is commonly implemented in extended frameworks, its application in porous molecular crystals remains challenging. Herein, we focus on utilizing porous molecular crystals, specifically tetraphenylethylene‐cored frameworks, as versatile platforms for tandem PSM reactions to customize organic fluorophores. The tailored skeleton design ensures both the formation of porous structures and the occurrence of tandem solid‐solution phase reactions while maintaining the solid state of reactants and products in each step. The inherent non‐covalent bonding nature of the frameworks facilitates processing and characterization, offering unparalleled advantages for porous networks. The accompanying solid‐state fluorescence transition from green to blue and then to green (or yellow) enables real‐time monitoring of tandem reactions and provides intuitive mechanistic insights. This phenomenon is exploited for the facile construction of a dynamic information encryption system using fluorescent quick response codes.

Synergetic experimental and theoretical investigation of molecular structure – Optical properties relationships of anthrazoline-based polymeric chains

The photoluminescence and UV–Vis absorption spectra of copolyamides containing 1,9-anthrazoline with para- and meta-[(substituted carbonyl)amino]phenyl-1-ene moieties in a polymer backbone were studied by a combination of experimental and theoretical approaches. The investigation was accomplished through time-dependent density functional theory electronic structure calculations of small-molecule models mimicking a polymer chain. Theoretical absorption and luminescence spectra of ten atomistic models were compared with corresponding experimental data, and the optical properties of two new luminescent molecules with bromine auxochrome were predicted. An analysis of the optical properties demonstrate an identical effect of the type and position of a substituent on the spectra for para- and meta-[(substituted carbonyl)amino]phenyl-1-ene moieties. It was found that the absorption and luminescence spectra of theoretical para-models demonstrate red shifts relative to the corresponding meta-ones. The same phenomenon was observed in experimental spectra of low-molecular-mass compounds and corresponding copolyamides in solution and bulk. Unique optical properties allow anthrazoline-based polymer compounds to be used in numerous advanced optoelectronic applications with desired optical and electronic characteristics.

Synthesis and characterization of a chiral spirobifluorene cyclic hexamer

Abstract A new chiral macrocycle 1-[6], consisting of six chiral spirobifluorene units linked in a cyclic arrangement, was successfully synthesized via a homo-coupling of the corresponding acyclic trimer. Notably, this chiral cyclic hexamer exhibited flexibility in solution, and both low-temperature nuclear magnetic resonance (NMR) experiments and density functional theory (DFT) calculations suggest that its stable structure is not the hexagonal D6-symmetric structure but rather the figure-eight-shaped D2-symmetric structure. In this D2-symmetric structure, the opposing bifluorenyl units are π-stacked, and it is suggested that this π-stacked region undergoes rapid dissociation and reformation at room temperature. The HOMO is distributed over the π-stacked region, with a HOMO-LUMO gap of 4.02 eV. The macrocycle exhibited strong violet fluorescence. The absorption dissymmetry factor |gabs| was 7.4 × 10−3, which is larger compared to the series of chiral smaller macrocycles 1-[n] (n = 3 to 5). Additionally, the CPL efficiency, indicated by a BCPL value of 189 M−1 cm−1, is relatively high among chiral organic luminescent molecules.

Atomically Fe(Ⅲ) anchored metal-organic frameworks-based fluorescent nanozyme for smartphone-adopted chemiluminescence-fluorescence dual-mode analysis of Uric acid

BackgroundChemiluminescence (CL) analysis is a promising analytical method with advantages including easy operation, high sensitivity and simple instrument. However, the single CL mode usually suffered from poor stability and reproducibility as a result of the flash-type nature of luminescent molecules, leading to false positive or negative results in practical applications. Dual-mode detection is an advanced sensing methodology that identifies analytes through independent output signals. This approach has the ability to circumvent the inherent constraints of individual sensing modes while integrating their respective strengths, thereby yielding a synergistic enhancement in the detection system. ResultsHerein, a chemiluminescence-fluorescence (FL) dual-mode analysis and imaging system is designed by constructing an atomically Fe(Ⅲ) anchored PCN-224 peroxidase-mimicking nanozyme (PCN-224/Fe(Ⅲ)) and achieve an ultrasensitive detection of Uric Acid (UA). The multifunctional PCN-224/Fe(Ⅲ) serves as a high-efficiency co-reaction promoter in the generation of reactive oxygen species (ROS) in both the CL and FL system, while also demonstrating exceptional capabilities as fluorescent nanoprobes. Ultimately, a smartphone-adopted CL imaging device was developed to achieve a visual CL detection through the design of portable paper-based chips. Besides, with the assistance of the TMB-mediated fluorescence energy resonance transfer, the fluorescent PCN-224/Fe(Ⅲ) nanoprobes exhibited good fluorescence detection performance for UA. The limit of detection was achieved as low as 2.45 × 10−10 M and 1.99 × 10−9 M in the CL and FL mode, respectively. SignificanceThis study engineered an atomically Fe(Ⅲ)- MOF-based multifunctional nanozyme and developed an innovative approach for creating CL-FL dual-mode analysis and imaging detection for UA. The proposed CL-FL dual-mode detection system not only provided a portable and sensitive method for UA detection but also offered valuable insights into the mechanism of the co-reaction promoter enhanced CL and FL analysis.

Room‐Temperature Single‐Molecule Infrared Imaging and Spectroscopy through Bond‐Selective Fluorescence

Infrared (IR) spectroscopy stands as a workhorse for exploring bond vibrations, offering a wealth of chemical insights across diverse frontiers. With increasing focus on the regime of single molecules, obtaining IR‐sensitive information from individual molecules at room temperature would provide essential information about unknown molecular properties. Here, we leverage bond‐selective fluorescence microscopy, facilitated by narrowband picosecond mid‐IR and near‐IR double‐resonance excitation, for high‐throughput mid‐IR structural probing of single molecules. We robustly capture single‐molecule images and analyze the combined polarization dependence, vibrational peaks, linewidths, and lifetimes of probe molecules with representative scaffolds. From bulk to single molecules, we find that vibrational lifetimes remain consistent, while linewidths are narrowed by approximately twofold and anisotropy becomes more pronounced. Additionally, unexpected peak shifts from single molecules were observed, attributed to the generation of new modes due to previously unexplored dimerization, supported by quantum chemistry calculations. These findings underscore the importance of infrared analysis on individual single molecules in ambient environments, offering molecular information crucial for functional imaging and the investigation of the fundamental properties and utilities of luminescent molecules.

Room-Temperature Single-Molecule Infrared Imaging and Spectroscopy through Bond-Selective Fluorescence.

Infrared (IR) spectroscopy stands as a workhorse for exploring bond vibrations, offering a wealth of chemical insights across diverse frontiers. With increasing focus on the regime of single molecules, obtaining IR-sensitive information from individual molecules at room temperature would provide essential information about unknown molecular properties. Here, we leverage bond-selective fluorescence microscopy, facilitated by narrowband picosecond mid-IR and near-IR double-resonance excitation, for high-throughput mid-IR structural probing of single molecules. We robustly capture single-molecule images and analyze the combined polarization dependence, vibrational peaks, linewidths, and lifetimes of probe molecules with representative scaffolds. From bulk to single molecules, we find that vibrational lifetimes remain consistent, while linewidths are narrowed by approximately twofold and anisotropy becomes more pronounced. Additionally, unexpected peak shifts from single molecules were observed, attributed to the generation of new modes due to previously unexplored dimerization, supported by quantum chemistry calculations. These findings underscore the importance of infrared analysis on individual single molecules in ambient environments, offering molecular information crucial for functional imaging and the investigation of the fundamental properties and utilities of luminescent molecules.

Novel electrochemiluminescence platform utilizing AuNPs@Uio-66-NH2 bridged luminescent substrates and aptamers for the detection of pesticide residues in Chinese herbal medicines

A large number of Chinese herbal medicines (CHMs) are included in daily recipes, but their pesticide residues have aroused more and more concerns. In this paper, an electrochemiluminescence aptasensor was constructed for the trace detection of acetamiprid (ACE) in Angelica sinensis and Lycium barbarum. Possessing a large specific surface area, UiO-66 was modified with amino groups to improve biocompatibility, and the addition of AuNPs allowed UiO-66-NH2 to catalyze the formation of excited states of luminescent molecules (TPrA⁎; Ru(bpy)32+⁎), and AuNPs@UiO-66-NH2 was used to bridge the aptamer (Au–S) and luminescent substrate (peptide bond). The conventional luminescent reagent Ru(bpy)32+ was doped with multi-walled carbon nanotubes (MWCNTs) to obtain a more powerful and stable light signal. After optimizing the experimental parameters, the aptasensor could give results in 10 min with a detection range from 1×10−2-1×104 nM and a lower limit of detection (LOD) of 0.8 pM. The LOD of the study was at least one order of magnitude lower than that of the fluorescence detection method. Furthermore, the accuracy of the aptasensor was validated for spiked recovery experiments.

Four‐Membered Ring‐Embedded Cycloarene Enabling Anti‐Aromaticity and Ultra‐Narrowband Emission

AbstractThe synthesis of fully fused π‐conjugated cycloarenes embedded with nonbenzenoid aromatics is challenging. In this work, the first example of four‐membered ring‐embedded cycloarene (MF2) was designed and synthesized in single‐crystal form by macrocyclization and ring fusion strategies. For comparison, single bond‐linked chiral macrocycle MS2 without two fused four‐membered rings and its linear‐shaped polycyclic benzenoid monomer L1 were also synthesized. The pronounced anti‐aromaticity of four‐membered rings significantly adjusts the electronic structures and photophysical properties of cycloarene, resulting in an enhancement of the photoluminescence quantum yield (PLQY) from 10.66 % and 10.74 % for L1 and MS2, respectively, to 54.05 % for MF2, which is the highest PLQY among the reported cycloarenes. Notably, owing to the embedded anti‐aromatic four‐membered rings that reduce structural displacements, MF2 exhibits an ultra‐narrowband emission with a single‐digit full‐width at half‐maximum (FWHM) of only 7 nm (0.038 eV), which sets a new record among all reported organic narrowband luminescent molecules, and represents the first example of ultra‐narrowband emission in conventional polycyclic aromatic hydrocarbons (PAHs) devoid of heteroatoms.

Two-dimensional-lattice-confined single-molecule-like aggregates.

Intermolecular distance largely determines the optoelectronic properties of organic matter. Conventional organic luminescent molecules are commonly used either as aggregates or as single molecules that are diluted in a foreigner matrix. They have garnered great research interest in recent decades for a variety of applications, including light-emitting diodes1,2, lasers3-5 andquantum technologies6,7, among others8-10. However, there is still a knowledge gap on how these molecules behave between the aggregation and dilution states. Here we report an unprecedented phase of molecular aggregate that forms in a two-dimensional hybrid perovskite superlattice with a near-equilibrium distance, which we refer to as a single-molecule-like aggregate (SMA). By implementing two-dimensional superlattices, the organic emitters are held in proximity, but, surprisingly, remain electronically isolated, thereby resulting in a near-unity photoluminescence quantum yield, akin to that of single molecules. Moreover, the emitters within the perovskite superlattices demonstrate strong alignment and dense packing resembling aggregates, allowing for the observation of robust directional emission, substantially enhanced radiative recombination and efficient lasing. Molecular dynamics simulations together with single-crystal structure analysis emphasize the critical role of the internal rotational and vibrational degrees of freedom of the molecules in the two-dimensional lattice for creating the exclusive SMA phase. This two-dimensional superlattice unifies the paradoxical properties of single molecules and aggregates, thus offering exciting possibilities for advanced spectroscopic and photonic applications.

Tandem Solid-Solution Phase Post-Synthetic Modification of Porous Molecular Crystals for In-Situ Generation of Fluorophores.

Conventional synthetic methods of organic luminescent molecules often involve labor-intensive solution-phase organic synthesis, which violate the principles of atom-economic transformation. Post-synthetic modification (PSM) offers a promising alternative, allowing direct transformation from one fluorophore to another. Although PSM is commonly implemented in extended frameworks, its application in porous molecular crystals remains challenging. Herein, we focus on utilizing porous molecular crystals, specifically tetraphenylethylene-cored frameworks, as versatile platforms for tandem PSM reactions to customize organic fluorophores. The tailored skeleton design ensures both the formation of porous structures and the occurrence of tandem solid-solution phase reactions while maintaining the solid state of reactants and products in each step. The inherent non-covalent bonding nature of the frameworks facilitates processing and characterization, offering unparalleled advantages for porous networks. The accompanying solid-state fluorescence transition from green to blue and then to green (or yellow) enables real-time monitoring of tandem reactions and provides intuitive mechanistic insights. This phenomenon is exploited for the facile construction of a dynamic information encryption system using fluorescent quick response codes.

Organic Mechanochromic Luminescent Materials with Self-Recovering Characters.

Recently, applied research on stimuli-responsive materials with luminescence-switching characteristics has been conducted in various fields. A representative phenomenon of stimuli-responsive luminescent materials is mechanochromic luminescence (MCL), which exhibits luminescent color change induced by mechanical stimuli such as grinding. These materials are among the most prominent candidates for security and sensing applications. Interestingly, some mechanochromic luminescent materials have shown self-recovery character, in which their original luminescent color can be recovered by just standing under ambient conditions after grinding. Although there are more and more reports of such materials in recent years, the fundamental principles of molecular design still remain elusive. In this concept, we summarize distinctive advances in mechanochromic luminescent materials with self-recovery according to the core structures of luminescent molecules. Controlling amorphous state by introducing substituents such as alkyl or polar groups is effective method to provide self-recovering properties.

1,1,2,2-Tetra(4-carboxylphenyl)ethylene-Based Metal-Organic Gel as Aggregation-Induced Electrochemiluminescence Emitter for the Detection of Aflatoxin B1 Based on Nanosurface Energy Transfer.

In this Letter, a sensitive DNA sensing platform was developed using an indium-ion-coordinated 1,1,2,2-tetra(4-carboxylphenyl)ethylene (TPE) metal-organic gel (In-MOG) as an aggregation-induced electrochemiluminescence (AIECL) emitter and nanosurface energy transfer (NSET) as an efficient quenching strategy for detecting aflatoxin B1 (AFB1), the most dangerous food toxin. The coordination occurred in indium ions, and carboxyl groups restricted the internal rotation and vibration of TPE molecules, forcing them to release photons via radiative transitions. The quenchers of microfluidic-produced gold nanoparticles were embedded in a long-tailed triangular DNA structure, where the quenching phenomenon aligned with the theory of ECL-NSET under the overlap of spectra and appropriate donor-acceptor spacing. The proposed analytical method showed a sensitive ECL response to AFB1 in the wide concentration range of 0.50-200.00 ng/mL with a limit of detection of 0.17 ng/mL. Experimental results confirmed that constraining luminescent molecules using coordination and bonding to trigger the AIECL phenomenon was a promising method to prepare signal labels for the trace detection of food toxins.

Chiral Tetrakis Eu(III) Complexes with Ammonium Cations for Improved Circularly Polarized Luminescence

AbstractLarge dissymmetry factor of the circularly polarized luminescence (gCPL) was observed in ligand and coordination tuned chiral tetrakis europium (Eu(III)) complexes with ammonium cations. The gCPL value was estimated to be −1.54, which is the largest among chiral luminescent molecules. Through photophysical measurements, single crystal X‐ray structural analyses and quantum chemical calculations, changes in the geometric and electronic structures were observed for a series of chiral tetrakis Eu(III) complexes which enhanced the gCPL value. The emission quantum yield and photosensitized energy transfer efficiencies of chiral Eu(III) complexes with ammonium cations were also larger than those of chiral Eu(III) complex with Cs+. Based on the systematic modifications and analyses for chiral tetrakis Eu(III) complex, effect of the ammonium cation on enhanced CPL brightness is reported.

Chiral Tetrakis Eu(III) Complexes with Ammonium Cations for Improved Circularly Polarized Luminescence.

Large dissymmetry factor of the circularly polarized luminescence (gCPL) was observed in ligand and coordination tuned chiral tetrakis europium (Eu(III)) complexes with ammonium cations. The gCPL value was estimated to be -1.54, which is the largest among chiral luminescent molecules. Through photophysical measurements, single crystal X-ray structural analyses and quantum chemical calculations, changes in the geometric and electronic structures were observed for a series of chiral tetrakis Eu(III) complexes which enhanced the gCPL value. The emission quantum yield and photosensitized energy transfer efficiencies of chiral Eu(III) complexes with ammonium cations were also larger than those of chiral Eu(III) complex with Cs+. Based on the systematic modifications and analyses for chiral tetrakis Eu(III) complex, effect of the ammonium cation on enhanced CPL brightness is reported.

Generation of pyridinylethylidenemalononitrile cyclic dimer: A facile route to multi-stimuli-responsive far-red/NIR luminogens

A simple synthetic strategy was successfully employed to develop NIR luminophores with switchable color-contrasting luminescence properties. D-A molecular motifs with dicyanovinylene appended pyridinyl moiety as the electron-withdrawing unit was not reported among luminescent molecules so far, owing to its unstable precursor compound pyridinylethylidenemalononitrile. By modifying the Knoevenagel condensation reaction pathways, the present work succeeded for the first time in identifying and crystallizing a novel cyclic dimerization product of the precursor compound. It further reports a new, simple, efficient synthetic route to achieve push-pull far-red/NIR emissive luminophores with the dicyanovinylene appended pyridinyl skeleton as the potent electron withdrawing unit. The enhanced charge transfer and the acidochromic characteristics make them suitable candidates in multi-stimuli-responsive smart materials with anti-counterfeiting applications.

Research progress in organic B/N-doped circularly polarized luminescent chiral molecules: synthesis, structure, and photophysical properties

Research progress in organic B/N-doped circularly polarized luminescent chiral molecules: synthesis, structure, and photophysical properties