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.     

Recent advances in supramolecular self-assembly and biological applications of luminescent alkynylplatinum(II) polypyridine complexes

Among various transition metal complexes, platinum(II) complexes are among one of the most extensively explored classes of metal complexes for supramolecular assembly, as their square-planar molecular geometry allows axial interactions between adjacent complex molecules and access to the formation of supramolecular assemblies with the aid of noncovalent Pt(II)⋯Pt(II) interactions. In the presence of external stimuli, alkynylplatinum(II) polypyridine complexes can self-assemble with alterations in their spectroscopic and luminescence properties. In light of their inherent advantages, including low-energy photoexcitation, red to near-infrared emission, large Stokes shifts, long phosphorescence lifetimes and high photostability, successful applications of alkynylplatinum(II) polypyridine complexes in the detection of biological analytes have been made possible. In this account, presented in part of the FACS Foundation Lecture, we introduce the basic concepts and our recent advances in the development of detection assays for various biomolecules based on luminescent alkynylplatinum(II) polypyridine complexes with selected examples.     

Pseudo-2D Layered Organic-Inorganic Manganese Bromide with a Near-Unity Photoluminescence Quantum Yield for White Light-Emitting Diode and X-Ray Scintillator

Eco-friendly lead-free organic–inorganic manganese halides (OIMHs) have attracted considerable attention in various optoelectronic applications because of their superior optical properties and flexible solution processibility. Herein, we report a novel pseudo-2D layered OIMH (MTP)₂MnBr₄ (MTP: methyltriphenylphosphonium), which exhibits intense green emission under UV/blue or X-ray excitation, with a near-unity photoluminescence quantum yield, high resistance to thermal quenching (I_{150 °C}=84.1 %) and good photochemical stability. These features enable (MTP)₂MnBr₄ as an efficient green phosphor for blue-converted white light-emitting diodes, demonstrating a commercial-level luminous efficiency of 101 lm W⁻¹ and a wide color gamut of 116 % NTSC. Moreover, these (MTP)₂MnBr₄ crystals showcase outstanding X-ray scintillation properties, delivering a light yield of 67000 photon MeV⁻¹, a detection limit of 82.4 nGy s⁻¹, and a competitive spatial resolution of 6.2 lp mm⁻¹ for X-ray imaging. This work presents a new avenue for the exploration of eco-friendly luminescent OIMHs towards multifunctional light-emitting applications.     

Metal Sulfide Nanoparticles: Precursor Chemistry

Fascination with and the need for evermore increasing efficiency, power, or strength have been the cornerstones for developing new materials and methods for their creation. Higher solar cell conversion efficiencies, increased battery storage power, and lightweight strong materials are some that have been at the forefront of attention for these efforts. Materials created for most applications start as simple chemical compounds. A study of how these chemicals have been used in the past can be used to create new materials and new methods of production. Herein, a class of materials that are valuable in a multitude of applications, metal sulfide nanoparticles, are examined, along with how they are being produced and how new methods can be established that will help to standardize and increase production capabilities. Precursor–solvent combinations that can be used to create metal sulfide nanoparticles in the gas phase are also explored.     

Recent advances in organic pressure-responsive luminescent materials

Pressure is a powerful tool to regulate the molecule aggregation and intermolecular interactions. Organic luminescent materials under high pressure can produce rich phenomena,which have many potential applications.     

Recent advances in organic pressure-responsive luminescent materials

Organic luminescent materials are very sensitive to external stimuli,such as pressure,temperature,and electric field.The luminescent properties of some organic luminescent materials significantly change under high pressure.Some materials may show luminescence discoloration,whereas some may exhibit luminescence enhancement.These properties have many potential applications in anticounterfeiting,force sensor,data recording and storage,and luminescent devices,thereby greatly attracting the attention of scientists.In this review,the progress of research on these materials at high pressure in recent years is summarized.     

白光型金属有机框架材料的最新研究进展

金属有机框架化合物（MOFs）是一类备受关注的多功能杂化材料,结构的多样性使其表现出各种发光性能。尤其是环境友好、使用寿命长、效率高的白光MOFs材料的出现为新型发光MOFs的设计和制备提供了契机。我们旨在总结白光MOFs的最新研究进展,着重对其合成方法及应用进行综述,主要包括镧系离子共掺杂、镧系元素封装或有机分子捕获等获得可调控的白光MOFs的方法及其在温度、分子和金属离子传感器等领域的潜在应用。同时,针对白光MOFs材料面临的挑战和未来发展也进行了梳理。以期引起设计和构建新型发光MOFs的研究人员的关注与兴趣。     

金属有机框架材料对Cr(Ⅵ)离子的吸附去除研究进展

重金属离子污染问题一直备受关注.开发利用多孔材料吸附去除水中重金属离子一直是材料、环境等相关学科领域的研究热点之一.金属有机框架材料(metal-organic frameworks,MOFs)是一类新型的多孔材料,具有结构多样、比表面积大、孔径可调、孔表面特征易设计调控等特点,在气体分离、催化、传感等领域表现出极大的...     

Gas Storage in Porous Molecular Materials

Molecules with permanent porosity in the solid state have been studied for decades. Porosity in these systems is governed by intrinsic pore space, as in cages or macrocycles, and extrinsic void space, created through loose, intermolecular solid-state packing. The development of permanently porous molecular materials, especially cages with organic or metal–organic composition, has seen increased interest over the past decade, and as such, incredibly high surface areas have been reported for these solids. Despite this, examples of these materials being explored for gas storage applications are relatively limited. This minireview outlines existing molecular systems that have been investigated for gas storage and highlights strategies that have been used to understand adsorption mechanisms in porous molecular materials.     

Luminescent complexes beyond the platinum group: the d10 avenue

Luminescent metal complexes are key materials for several applications such as lighting, analytical probes, and lasers. In many cases compounds based on precious (i.e. platinum group) and rare earth metals are utilized, which are often rather expensive and environmentally problematic. In recent years, interest is growing in luminescent complexes based on less traditional but more abundant and cheaper metal elements. In this scenario compounds of metals with a d10 electronic configuration are playing a prominent role, also thanks to the versatility of their luminescent levels which can be of ligand centred, charge transfer or, in the case of polynuclear compounds, even metal-centred nature. Here we focus on some selected examples of Cu(I), Ag(I), Au(I), Zn(II) and Cd(II) luminescent complexes to suggest some possible routes towards promising and unprecedented emitting materials.     

近红外稀土荧光在功能材料领域的研究进展

稀土近红外荧光材料具有特征发射峰尖锐、光稳定性好和毒性低等特点。近年来,稀土近红外荧光材料在光纤通讯、激光系统、生物分析传感器及生物成像等方面的应用价值日渐突显,引起了研究者们的极大关注。特别是稀土近红外荧光材料已发展成一种新兴的荧光标记材料,并有希望替代有机染料和量子点应用于生物分析和医学成像。基于稀土近红外发光的荧光探针具有低自荧光背景、宽斯托克斯位移、强抑制光漂白、深层穿透组织和短暂分辨的优势,有潜力成为高灵敏度、高选择性的检测手段。利用稀土离子制备的各种荧光材料,如上转换纳米晶、介孔材料、脂基胶体、离子液体、离子胶体、金属有机框架等,由于荧光敏化机理不同,其近红外荧光性能也各有千秋。然而,稀土近红外荧光的真正挑战仍是提高近红外发光的量子效率。本文结合近红外荧光领域的最新进展,综述了不同的稀土近红外荧光设计思路,介绍了各种近红外稀土荧光功能材料,阐述了稀土离子在近红外荧光功能材料中的优势,并展望了稀土近红外荧光材料的发展前景。     

Luminescent nanoscale metal–organic frameworks for chemical sensing

Metal–organic frameworks(MOFs) are a fascinating class of crystalline materials constructed from selfassembly of metal cations/clusters and organic ligands. Both metal and organic components can be used to generate luminescence, and can further interact via antenna effect to increase the quantum yield,providing a versatile platform for chemical sensing based on luminescence emission. Moreover, MOFs can be miniaturized to nanometer scale to form nano-MOF(NMOF) materials, which exhibit many advantages over conventional bulk MOFs in terms of the facile tailorability of compositions, sizes and morphologies, the high dispersity in a wide variety of medium, and the intrinsic biocompatibility. This review will detail the development of NMOF materials as chemical sensors, including the synthetic methodologies for designing NMOF sensory materials, their luminescent properties and potential sensing applications.     

压致变色聚集诱导发光材料

聚集诱导发光化合物分子具有特殊的螺旋桨形扭曲构象结构, 导致其很难在结晶状态下进行紧密堆砌, 使得其结晶结构容易在外力的作用发生改变, 致使其分子能级水平和发光光谱发生变化, 产生压致发光变色现象. 因此, 聚集诱导发光化合物是压致发光变色材料的一个重要来源. 压致变色聚集诱导发光材料是一类重要的压致发光变色材料, 其既具有压致发光变色的性能, 又具有聚集诱导发光的性能. 它是一类智能材料, 在应力传感、商标防伪和发光器件等领域具有重要的潜在应用, 近年来受到人们极大的关注. 本文分类介绍了近年来压致变色聚集诱导发光材料的研究进展.     

Development of Optical Sensors Based on Luminescent Transition-Metal Complexes

Luminescence-based optical sensors are becoming increasingly important particularly in the area of fibber optic sensors. Most luminescence sensors detect analyses based on the change in luminescent intensity or excited-state lifetime of the sensing material as a function of analyst concentration. Luminescent materials with long excited-state lifetime are essential for the development of inexpensive sensors because it is much simpler and less expensive to measure lifetime in microseconds than in nanoseconds. Luminescent dyes with absorption in the visible region would allow the use of inexpensive light sources such as light emitting diodes (LEDs). Recent studies indicate that luminescent transition metal complexes, especially those with platinum group metals, have desirable spectral characteristics and features including long excited state lifetimes, high luminescence quantum yields and intense visible absorptions. They also tend to be thermally, chemically and photochemically robust. We have been investigating new luminescent sensor materials with the aims to understand the behaviour of luminescent materials in polymer and gel support and to develop new sensor materials with desirable properties.     

Luminescent metal complexes of d6, d8 and d10 transition metal centres

This highlight focuses on various luminescent complexes with different transition metal centres of d(6), d(8) and d(10) electronic configurations. Through the systematic study on the variation of ligands, structural and bonding modes of different metal centres, the structure-property relationships of the various classes of luminescent transition metal complexes can be obtained. With the knowledge and fundamental understanding of their photophysical behaviours, their electronic absorption and luminescence properties can be fine-tuned. Introduction of supramolecular assembly with hierarchical complexity involving non-covalent interactions could lead to research dimensions of unlimited possibilities and opportunities. The approach of "function by design" could be employed to explore and exploit the potential applications of such luminescent transition metal complexes for future development of luminescent materials.     

Two-dimensional MOFs: Design & Synthesis and Applications

For the past few years, two-dimensional materials have attracted widespread attention owing to their special properties and potential applications. It is well-known that graphene, transition metal disulfide compounds (TMDC), carbon nitride, transition metal carbonitrides (Mxenes), silene and hexagonal boron nitride are typical two-dimensional materials. Compared with these traditional two-dimensional materials, two-dimensional MOF is favored by numerous researchers because of its unique structure. Based on the unique metal ion and organic ligand coordination of MOF and two-dimensional layered structure, the applications of two-dimensional MOF were getting serious, including catalysis, supercapacitor, gas adsorption/separation, sensors and so on. This review presents a relatively comprehensive summary of the design & synthesis and applications of two-dimensional MOF over the past few years. Furthermore, the opportunities and challenges have been discussed to supply a promising prospect to this field.     

Recent progress of luminescent metal complexes with photochromic units

Photo-responsive molecules have been studied extensively because of their light irradiation abilities that enable modulation of certain physical and chemical properties in emerging molecular electronic and photonic devices. For advanced photonic applications, photochromic metal complexes that have photochromic units as the photo-responsive ligand are highly desirable, as they allow improvement of the photochromic properties and their photo-switching functionality. This article focuses on recent progress in luminescent metal complexes with photochromic units. Luminescence-switching properties of photochromic metal complexes depend on characteristic electronic transitions. The electronic transitions of photochromic metal complexes can be divided into three categories: (1) π–π* transition of the ligand, (2) metal to ligand charge transfer (MLCT) in transition-metal complex, and (3) f–f transition in lanthanide complex. Luminescence modulation using various metal complexes with photochromic units has been studied extensively in recent years, and various applications for future molecular switching devices are expected in the field of advanced photonics. Based on the literature and our studies on luminescent metal complexes with photochromic units, we report on the recent progress of luminescent metal complexes with photochromic units.     

Bimetallic Au2Cu6 Nanoclusters: Strong Luminescence Induced by the Aggregation of Copper(I) Complexes with Gold(0) Species

The concept of aggregation‐induced emission (AIE) has been exploited to render non‐luminescent Cu^ISR complexes strongly luminescent. The Cu^ISR complexes underwent controlled aggregation with Au⁰. Unlike previous AIE methods, our strategy does not require insoluble solutions or cations. X‐ray crystallography validated the structure of this highly fluorescent nanocluster: Six thiolated Cu atoms are aggregated by two Au atoms (Au₂Cu₆ nanoclusters). The quantum yield of this nanocluster is 11.7 %. DFT calculations imply that the fluorescence originates from ligand (aryl groups on the phosphine) to metal (Cu^I) charge transfer (LMCT). Furthermore, the aggregation is affected by the restriction of intramolecular rotation (RIR), and the high rigidity of the outer ligands enhances the fluorescence of the Au₂Cu₆ nanoclusters. This study thus presents a novel strategy for enhancing the luminescence of metal nanoclusters (by the aggregation of active metal complexes with inert metal atoms), and also provides fundamental insights into the controllable synthesis of highly luminescent metal nanoclusters.     

Side‐chain functionalized polymers containing bipyridine coordination sites: Polymerization and metal‐coordination studies

Monomers containing (trisbipyridine) ruthenium(II), (bisbipyridine) palladium(II), and heteroleptic ruthenium complexes were synthesized and polymerized via ruthenium‐catalyzed ring‐opening metathesis polymerization in nonpolar solvents. The solubility of the resulting polyelectrolytes in nonpolar solutions could be tuned by alkyl functionalization of the ligands around the metal centers. These polymers are the first polynorbornenes containing a 2,2′‐bipyridine‐based metal complex at each repeating unit and might be used in numerous applications, including luminescent and electroluminescent materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2973–2984, 2004     

Mild Synthesis of Polychlorinated Arenes for Efficient Organic Light-emitting Diodes with Dual Thermally Activated Delayed Fluorescence

Polychlorinated (hetero)arenes have shown great promise for organic optoelectronics applications. However, the harsh synthetic routes for polychlorinated compounds and the possible luminescence quenching from the compact intermolecular π–π stacking induced by chlorine atoms limit their investigations and applications in luminescent materials. Herein, two isomeric polychlorinated polycyclic aromatic hydrocarbon (PAH) compounds JY-1-Cl and JY-2-Cl consisting of rigidified aryl ketones and amine are designed and synthesized under mild conditions through nucleophilic chlorination intermediated by an electron donor-acceptor complex. Among them, as a result of the strong π–π interactions induced by chlorine atoms, JY-2-Cl exhibits bright monomer and dimer emissions with dual thermally activated delayed fluorescence (TADF) characters. Notably, compared with the non-chlorinated compounds, a high photoluminescence quantum yield is maintained after introducing multiple chlorine atoms into JY-2-Cl . The first dual-TADF organic light-emitting diodes are also successfully fabricated with maximum external quantum efficiency as high as 29.1 % by employing JY-2-Cl as emitter. This work presents a new paradigm and synthesis of polychlorinated amine-carbonyl PAHs and demonstrates the great potential of the chlorinated materials for luminescent applications.