Molecular Design,Circularly Polarized Luminescence,and Helical Self‐Assembly of Chiral Aggregation‐Induced Emission Molecules

Aggregation‐induced emission luminogens (AIEgens) are a new class of luminophors, which are non‐emissive in solution, but emit intensively upon aggregation. By properly designing the chemical structures of the AIEgens, their aggregation process can be tuned towards a desired direction to give diverse novel luminescent architectures of micelles, rods, and helical fibers. AIEgens represent a kind of promising building block for the fabrication of luminescent micro/nanostructures with controllable morphologies. In this review, we describe our recent work in this research area, focusing on the molecular design, circularly polarized luminescence properties, and helical self‐assembly behavior of AIEgens.     

Photo-controllable Luminescence from Radicals Leading to Ratiometric Emission Switching via Dynamic Intermolecular Coupling

The development of photoinduced luminescent radicals with dynamic emission color is still challenging. Herein we report a novel molecular radical system (TBIQ) that shows photo-controllable luminescence, leading to a wide range of ratiometric color changes via light excitation. The conjugated skeleton of TBIQ is decorated with steric-demanding tertiary butyl groups that enable appropriate intermolecular interaction to make dynamic intermolecular coupling possible for controllable behaviors. We reveal that the helicenic pseudo-planar conformation of TBIQ experiences a planarization process after light excitation, leading to more compactly stacked supermolecules and thus generating radicals via intermolecular charge transfer. The photo-controllable luminescent radical system is employed for a high-level information encryption application. This study may offer unique insight into molecular dynamic motion for optical manufacturing and broaden the scope of smart-responsive materials for advanced applications.     

Self-twisting for macrochirality from an achiral asterisk molecule with fluorescence-phosphorescence dual emission

A self-progressing chiral self-assembly form an achiral and C₆-symmetric molecule, resulting in a chiral amplification with prolonging the time. The system shows three distinct luminescent colors with the change of time in the same solution system.     

Luminescent metal alkynyls - from simple molecules to molecular rods and materials

This review describes the design and synthesis of a number of luminescent transition metal alkynyls by this laboratory. The luminescence properties of the complexes have been studied and their emission origin elucidated. Some of these complexes have been shown to be ideal building blocks for the design and construction of luminescent molecular rods and materials, in which the luminescence properties can be readily tuned by changing the alkynyl ligands. Some of them also exhibited luminescence switching behaviour with the “ON-OFF” luminescence states modulated by redox processes, metal ion-binding or solvent composition.     

How far are luminescence properties predictable?

Our knowledge of the luminescence of isolators has increased considerably during the past decade. As a consequence it has become possible to understand the luminescence of technically important phosphors and even to predict efficient luminescent materials. We first illustrate how emission spectra of a given activator can be varied by changing the host lattice. Second we consider the factors influencing the luminescent efficiency. Using a single-configurational coordinate model, we have performed calculations on a model system. These illustrate which factors are important for efficiency. Some clear results are reported. Finally, we discuss the mobility of excitation energy. In some phosphors the excitation is highly mobile even at low temperatures. As a consequence emission originates from centers which trap the excitation energy. In other phosphors this mobility is low, and at low temperatures emission occurs from the regular luminescence centers. At higher temperatures the excitation energy can become mobile because of thermal activation.     

Luminescent chemosensors based on semiconductor quantum dots

Semiconductor quantum dots are inorganic nanoparticles with unique photophysical properties. In particular, their huge one- and two-photon absorption cross sections, tunable emission bands and excellent photobleaching resistances are stimulating the development of luminescent probes for biomedical imaging and sensing applications. Indeed, electron and energy transfer processes can be designed to switch the luminescence of semiconductor quantum dots in response to molecular recognition events. On the basis of these operating principles, the presence of target analytes can be transduced into detectable luminescence signals. In fact, luminescent chemosensors based on semiconductor quantum dots are starting to be developed to detect small molecules, monitor DNA hybridization, assess protein-ligand complementarities, test enzymatic activity and probe pH distributions. Although fundamental research is still very much needed to understand further the fundamental factors regulating the behavior of these systems and refine their performance, it is becoming apparent that sensitive probes based on semiconductor quantum dots will become invaluable analytical tools for a diversity of applications in biomedical research.     

Mechanically controlled FRET to achieve high-contrast fluorescence switching

Organic luminescent materials with the ability to reversibly switch the luminescence when subjected to external stimuli have attracted considerable interest in recent years. However, luminescent materials with mechanochromic and photochromic dual-responsive properties are rarely reported. Hererin, we designed and synthesized a molecule P1 with dipeptide as a spacer to link rhodamine B and spiropyran moieties. P1 exhibited efficient photochromic properties both in solution and solid state. High-contrast independent fluorescence switch was also realized under the stimulus of external force. Moreover, two-step ring opening reaction and subsequent fluorescence resonance energy transfer process between the donor-acceptor pairs within one single molecule achieved successive color switch by mechanical control. Therefore, this behavior of P1 made it a promising candidate for high-contrast and sensitive optical recording and mechanical sensing system.     

Luminescence of lanthanide complexes: From fundamental to prospective approaches related to water- and molecular-stimuli

Luminescent lanthanide (Ln) complexes are attracted much attention because of their stable emission colors induced by the photo-antenna effect through the photo-excited energy transfer from aromatic ligands to Ln ions. Here, we will introduce some systems of luminescent Ln complexes with metastable states with the phase transition induced by water and other small molecules, the relative arrangement of hydrogel formation and Ln luminescence enhancement, and the diversity of the thin air-water interface. The energy donor levels in each system should be designed to sensitize Ln-luminescence with the consideration of media, interaction and assembling. Luminescence quenching of Ln complexes in water is a point that should be considered for the development of materials and for the purpose of bio-related materials. Then, the principle of the change in luminescence intensity by the effect of water molecules is described, and the estimation of a hydrated structure of the complex is estimated using the luminescence lifetimes in H₂O and D₂O. The molecular arrangement of these crystals changes under the vapor-stimuli, and the coloration and luminescence may be enhanced. Some interesting cases of luminescent Ln complexes with the crystal-to-crystal phase transitions will be introduced with the vapor adsorption. Hydrogels are mostly water by volume; a system in which Ln luminescence is maintained implies that Ln ions are placed in hydrophobic positions in self-assemblies with strong luminescence. The formation of thin films at the molecular level and their Ln luminescence properties are introduced. For example, when a monolayer of a surface-active Ln complex is formed at the air-water interface, the repeated accumulation of the flexible film forms a metastable structure with a regular structure different from that of a crystal, and no water is incorporated into the film. These can not only derive circularly or linearly polarized light, but also take in other molecules and change the emission. Finally, we will suggest the prospects for the development of Ln complexes.     

Principal component analysis calibration method for dual-luminophore oxygen and temperature sensor films: application to luminescence imaging

Oxygen sensor films are frequently used to image air-pressure distributions on surfaces in aerodynamic wind tunnels. In this application, the sensor film is referred to as a pressure-sensitive paint (PSP). A Stern-Volmer calibration is used to relate the emission intensity ratio of a long-lifetime luminescent dye (the pressure-sensitive luminophore, PSL) to surface air pressure. A major problem in PSP measurements arises because the Stern-Volmer calibration of the PSL's emission varies with temperature. To correct for the temperature dependence, a second luminescent dye that has an emission that varies with temperature (the temperature-sensitive luminophore, TSL) is incorporated into the sensor film. With such a dual-luminophore PSP (DL-PSP), it is possible to measure the surface-temperature distribution with the TSL emission, and this information is then used to correct the temperature dependence of the PSL's pressure response. In the present article, we report the application of a DL-PSP to obtain high-resolution air-pressure distributions on a surface that is subjected to a 20 degrees C temperature gradient. Two different calibration methods are used to generate surface-temperature and air-pressure distributions from the luminescence imaging data, and a quantitative comparison of the results obtained from the two methods is provided. The first method is based on an intensity-ratio calibration that uses luminescence images collected at two wavelengths, one corresponding to the TSL emission and the second corresponding to the PSL emission. The second method is based on principal component analysis (PCA) of luminescence images obtained at four wavelengths throughout the spectral region of the TSL and PSL emission (hyperspectral imaging, 550-750 nm). The results demonstrate that the PCA method allows the measurement of surface air pressure with higher accuracy and precision compared to those of the intensity-ratio method. The improvement is especially significant at pressures near 1 atm, where the temperature interference is most pronounced. Surface-pressure distributions are measured with comparable accuracy and precision with the two methods.     

An Extended NIR-II Superior Imaging Window from 1500 to 1900 nm for High-Resolution In Vivo Multiplexed Imaging Based on Lanthanide Nanocrystals

High-resolution in vivo optical multiplexing in second near-infrared window (NIR-II, 1000–1700 nm) is vital to biomedical research. Presently, limited by bio-tissue scattering, only luminescent probes located at NIR-IIb (1500–1700 nm) window can provide high-resolution in vivo multiplexed imaging. However, the number of available luminescent probes in this narrow NIR-IIb region is limited, which hampers the available multiplexed channels of in vivo imaging. To overcome the above challenges, through theoretical simulation we expanded the conventional NIR-IIb window to NIR-II long-wavelength (NIR-II-L, 1500–1900 nm) window on the basis of photon-scattering and water-absorption. We developed a series of novel lanthanide luminescent nanoprobes with emission wavelengths from 1852 nm to 2842 nm. NIR-II-L nanoprobes enabled high-resolution in vivo dynamic multiplexed imaging on blood vessels and intestines, and provided multi-channels imaging on lymph tubes, tumors and intestines. The proposed NIR-II-L probes without mutual interference are powerful tools for high-contrast in vivo multiplexed detection, which holds promise for revealing physiological process in living body.     

Piezochromism in Dynamic Three-Dimensional Covalent Organic Frameworks

Piezochromic materials with pressure-dependent photoluminescence tuning properties are important in many fields, such as mechanical sensors, security papers, and storage devices. Covalent organic frameworks (COFs), as an emerging class of crystalline porous materials (CPMs) with structural dynamics and tunable photophysical properties, are suitable for designing piezochromic materials, but there are few related studies. Herein, we report two dynamic three-dimensional COFs based on aggregation-induced emission (AIE) or aggregation-caused quenching (ACQ) chromophores, termed JUC-635 and JUC-636 (JUC=Jilin University China), and for the first time, study their piezochromic behavior by diamond anvil cell technique. Due to the various luminescent groups, JUC-635 has completely different solvatochromism and molecular aggregation behavior in the solvents. More importantly, JUC-635 with AIE effect exhibits a sustained fluorescence upon pressure increase (≈3 GPa), and reversible sensitivity with high-contrast emission differences (Δλ_em=187 nm) up to 12 GPa, superior to other CPMs reported so far. Therefore, this study will open a new gate to expand the potential applications of COFs as exceptional piezochromic materials in pressure sensing, barcoding, and signal switching.     

A Luminescent Dye@MOF Platform: Emission Fingerprint Relationships of Volatile Organic Molecules

Self‐assembly of luminescent moieties into porous metal–organic frameworks (MOFs) has generated many luminescent platforms for probing volatile organic molecules (VOMs). However, most of those explored thus far have only been based on the luminescence intensity of one transition, which is not efficient for probing different VOMs. We have synthesized a luminescent MOF material containing 1D nanotube channels, and further developed a luminescent dye@MOF platform to realize the probing of different VOMs by tuning the energy transfer efficiency between two different emissions. The dye@MOF platform exhibits excellent fingerprint correlation between the VOM and the emission peak‐height ratio of ligand to dye moieties. The dye@MOF sensor is self‐calibrating, stable, and instantaneous, thus the approach should be a very promising strategy to develop luminescent materials with unprecedented practical applications.     

Dual sensing of oxygen and temperature using quantum dots and a ruthenium complex

A scheme for the simultaneous determination of oxygen and temperature using quantum dots and a ruthenium complex is demonstrated. The luminescent complex [Ru(II)-tris(4,7-diphenyl-1,10-phenanthroline)]²⁺ is immobilized in a non-hydrolytic sol-gel matrix and used as the oxygen sensor. The temperature information is provided by the luminescent emission of core-shell CdSe-ZnS semiconductor nanocrystals immobilized in the same material. Measurements of oxygen and temperature could be performed with associated errors of ±2% of oxygen concentration and ±1 °C, respectively. In addition, it is shown that while the dye luminescence intensity is quenched both by oxygen and temperature, the nanocrystals luminescent emission responds only to temperature. Results presented demonstrate that the combined luminescence response allows the simultaneous assessment of both parameters using a single optical fiber system. In particular, it was shown that a 10% error in the measured oxygen concentration, induced by a change in the sample temperature, could be compensated using the nanocrystals temperature information and a correction function.     

An Anionic Interpenetrated Zeolite‐Like Metal–Organic Framework Composite As a Tunable Dual‐Emission Luminescent Switch for Detecting Volatile Organic Molecules

The luminescent MOF [(CH₃)₂NH₂]₂[(Zn₂O)L]?5 DMF (NENU‐519, NENU=Northeast Normal University) with a zeolite BCT topology was successfully synthesized. It is a rare example of a two‐fold interpenetrated framework with a zeolite topology. NENU‐519 demonstrates the ability to selectively adsorb cationic dyes. Furthermore we developed Rh6@NENU‐519 (Rh6=Rhodamine 6G) as a dual‐emitting sensor for probing different volatile organic molecules (VOMs) due to an energy transfer between L and the dye. The composite can be used to distinguish the isomers of o‐, m‐, and p‐xylene and ethylbenzene using the emission‐peak‐height ratios of L to the dye as detectable signals, in which the readout signals are involved in the interactions between the dye@MOF composite and the guest analytes. Moreover, Rh6@NENU‐519 can serve as a luminescent switch for the detection of different aromatic compounds, like benzene, benzene substituted with different groups, and pyridine. In other words, the Rh6@NENU‐519 composite can be used as molecular decoder of the structural information of different VOMs into recognizable luminescent signals. Hopefully this work will open a new corridor to develop luminescent guest@MOF composites as sensors for practical applications.     

Magnetoluminescence in a Photostable,Brightly Luminescent Organic Radical in a Rigid Environment

We investigated the emission properties of a photostable luminescent organic radical, (3,5‐dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl radical (PyBTM), doped into host molecular crystals. The 0.05 wt %‐doped crystals displayed luminescence attributed to a PyBTM monomer with a room‐temperature emission quantum yield of 89 %, which is exceptionally high among organic radicals. The 10 wt %‐doped crystals exhibited both PyBTM monomer and excimer‐centered emission bands, and the intensity ratio of these two bands was modulated drastically by applying a magnetic field of up to 18 T at 4.2 K. This is the first observation of a magnetic field affecting the luminescence of organic radicals, and we also proposed a mechanism for this effect.     

Magnetoluminescence in a Photostable,Brightly Luminescent Organic Radical in a Rigid Environment

We investigated the emission properties of a photostable luminescent organic radical, (3,5‐dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl radical (PyBTM), doped into host molecular crystals. The 0.05 wt %‐doped crystals displayed luminescence attributed to a PyBTM monomer with a room‐temperature emission quantum yield of 89 %, which is exceptionally high among organic radicals. The 10 wt %‐doped crystals exhibited both PyBTM monomer and excimer‐centered emission bands, and the intensity ratio of these two bands was modulated drastically by applying a magnetic field of up to 18 T at 4.2 K. This is the first observation of a magnetic field affecting the luminescence of organic radicals, and we also proposed a mechanism for this effect.     

Highly Luminescent Inks: Aggregation‐Induced Emission of Copper–Iodine Hybrid Clusters

Aggregation‐induced emission (AIE) is an attractive phenomenon in which materials display strong luminescence in the aggregated solid states rather than in the conventional dissolved molecular states. However, highly luminescent inks based on AIE are hard to be obtained because of the difficulty in finely controlling the crystallinity of AIE materials at nanoscale. Herein, we report the preparation of highly luminescent inks via oil‐in‐water microemulsion induced aggregation of Cu–I hybrid clusters based on the highly soluble copper iodide‐tris(3‐methylphenyl)phosphine (Cu₄I₄(P‐(m‐Tol)₃)₄) hybrid. Furthermore, we can synthesize a series of AIE inks with different light‐emission colors to cover the whole visible spectrum range via a facile ligand exchange processes. The assemblies of Cu–I hybrid clusters with AIE characteristics will pave the way to fabricate low‐cost highly luminescent inks.     

Host Differential Sensitization toward Color/Lifetime-Tuned Lanthanide Coordination Polymers for Optical Multiplexing

Optical multiplexing based on luminescent materials with tunable color/lifetime has potential applications in information storage and security. However, the available tunable luminescent materials reported so far still suffer from several drawbacks of low efficiency or poor stability, thus restraining their further applications. Herein, we demonstrate a strategy to develop efficient and stable lanthanide coordination polymers (LCPs) with tunable luminescence as a new option for optical multiplexing. Their multicolor emission from green to red and naked-eye-sensitive green emission with tunable lifetime (from ca. 300 to ca. 600 μs) can be controlled by host differential sensitization and energy transfer between lanthanide ions. The quantum efficiencies of developed samples range from around 20 % to 46 % and the luminescence intensity/lifetime appear quite stable in polar solvents up to ten weeks. Furthermore, with the aid of inkjet printing and concepts of luminescence lifetime imaging and time-gated imaging, we illustrate their promising applications of information storage and security in spatial and temporal domains.     

Understanding the Unconventional Effects of Halogenation on the Luminescent Properties of Oligo(Phenylene Vinylene) Molecules

It is commonly known that halogenation tends to decrease the luminescence quantum yield of an organic dye, owing to the high electronegativity and heavy‐atom effect of the halogen atom. However, based on an investigation of the effects of halogenation on the luminescence of the oligo(phenylene vinylene) (OPV) framework, we demonstrate that halogenation can have positive impact on the solid‐state fluorescence and electrochemiluminescence (ECL) properties of OPV derivatives. The chlorinated OPV exhibits a very high solid‐state fluorescence quantum yield (91 %), whilst the brominated analogue gives the highest ECL emission intensity. Time‐dependent density functional theory calculations, natural bond orbital analysis, and natural transition orbital analysis were performed to assist the understanding of the origin of these positive halogenation effects, which provide insight into the rational design of highly luminescent halogenated organic materials for solid‐state devices and ECL applications.     

Cluster Linker Approach: Preparation of a Luminescent Porous Framework with NbO Topology by Linking Silver Ions with Gold(I) Clusters

A cluster‐based luminescent porous metal–organic framework has been constructed through a “cluster linker” approach. The luminescent gold(I) cluster, prefunctionalized with pyrazinyl groups, was used as a cluster linker, similar to an organic linker, to connect silver ions in order to form a 3D framework. 1D channels with 1.1 nm diameter were observed in the framework. The cluster with its intrinsic luminescence was incorporated into a porous framework to give a luminescent bifunctional NbO net. This MOF shows solvatochromic behavior, and the interactions between solvent molecules and silver ions inside the channels account for the changes in absorption and emission spectra.