Applications of luminescent inorganic and organometallic transition metal complexes as biomolecular and cellular probes

The rich photophysical properties of luminescent inorganic and organometallic transition metal complexes, such as their intense, long-lived, and environment-sensitive emission, render them excellent candidates for biological and cellular studies. In this Perspective, we review examples of biological probes derived from luminescent transition metal complexes with a d(6), d(8), or d(10) metal center. The design of luminescent covalent labels and noncovalent probes for protein molecules is discussed. Additionally, the recent applications of these complexes as cellular probes and bioimaging reagents are described. Emphasis is put on the structural features, photophysical behavior, biomolecular interactions, cellular uptake, and intracellular localization properties of luminescent transition metal complexes.     

DNA modified with metal complexes: Applications in the construction of higher order metal–DNA nanostructures

DNA has recently emerged as a useful building block for higher order nanostructures, such as extended two-dimensional surfaces and discrete two- and three-dimensional structures. Transition metal complexes can introduce functionality to these otherwise passive nanostructures. This review examines the synthetic strategies used to introduce metals in a site-specific manner to DNA: either by attaching preformed metal complexes to DNA, or by metal coordination to unmodified or modified DNA. The applications of metal–DNA complexes in building higher order nanostructures and the utility of attaching luminescent or electrochemical labels are discussed.     

Design of luminescent iridium(III) and rhenium(I) polypyridine complexes as in vitro and in vivo ion,molecular and biological probes

Many luminescent transition metal polypyridine complexes display intense and long-lived triplet charge-transfer and intraligand transition emission with a large Stokes’ shift. These properties render them promising candidates as luminescent probes for ions, DNA, peptides, proteins and other biological entities. In this review article, we have summarised recent reports on ion, molecular and biological probes derived from luminescent rhenium(I) and iridium(III) polypyridine complexes. These complexes have been appended with different recognition moieties that interact with ions and biological molecules. The recognition is reflected by a change of spectroscopic and/or photophysical properties of the probes. The use of these complexes as cellular probes and imaging reagents has also been discussed.     

Biomedical applications of macrocyclic ligand complexes

Macrocyclic chelators can form highly stable complexes with transition metals and lanthanides. In this review, the recent advances towards biomedical applications of macrocyclic complexes are outlined. The use of such complexes in imaging as MRI contrast agents, radiopharmaceuticals and luminescent probes is discussed. The considerable scope for future development of novel metal based therapeutics based on protein binding, targeting of radioisotopes or dual function agents is also highlighted.     

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.     

Interactions of Transition-Metal-Complex Photosensitizers with Polymers and Organized Media

The interactions of luminescent platinum metal complexes with a variety of organized media, including micelles, cyclodextrins, and solid polymers, are described. In particular, Ru(II), Os(II), and Re(I) complexes with α-diimine ligands are discussed. Applications of these systems, including luminescence quantum counters, singlet oxygen generators, and a luminescent oxygen sensor, are described. Useful tools for studying these systems are described; these include a deuterium isotope method for measuring the degree of solvent exposure of bound sensitizers, excited-state-lifetime titrations for examining the compositions of systems, and spectral fitting and temperature profiles for probing excited state ordering and energies.     

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.     

Bioactive Luminescent Transition‐Metal Complexes for Biomedical Applications

The serendipitous discovery of the anticancer drug cisplatin cemented medicinal inorganic chemistry as an independent discipline in the 1960s. Luminescent metal complexes have subsequently been widely applied for sensing, bio‐imaging, and in organic light‐emitting diode applications. Transition‐metal complexes possess a variety of advantages that make them suitable as therapeutics and as luminescent probes for biomolecules. It is thus highly desirable to develop new luminescent metal complexes that either interact with DNA through different binding modes or target alternative cellular machinery such as proteins as well as to provide a more effective means of monitoring disease progression. In this Review, we highlight recent examples of biologically active luminescent metal complexes that can target and probe a specific biomolecule, and offer insights into the future potential of these compounds for the investigation and treatment of human diseases.     

Electroluminochromic Materials and Devices Based on Metal Complexes

Electroluminochromism (ELC) refers to an interesting phenomenon exhibited by a material whose luminescent properties can be reversibly modulated under an electrical stimulus. Such a luminescence‐switching property has been widely used in various organic optoelectronic devices because it can simultaneously detect electrical and optical signals. Metal complexes are the promising candidates for ELC materials due to their sensitivity to an electrical stimulus. Herein, recent progress on electroluminochromic materials and devices based on various metal complexes has been summarized. Meanwhile, the applications of these complexes in data recording and security protection have also been discussed. Finally, a brief conclusion and outlook are presented, pointing out that the development of electroluminochromic metal complexes with excellent performance is important because they play a vital role in future intelligent optoelectronic devices.     

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.     

Anticancer and Antibiotic Rhenium Tri- and Dicarbonyl Complexes: Current Research and Future Perspectives

Organometallic compounds are increasingly recognized as promising anticancer and antibiotic drug candidates. Among the transition metal ions investigated for these purposes, rhenium occupies a special role. Its tri- and dicarbonyl complexes, in particular, attract continuous attention due to their relative ease of preparation, stability and unique photophysical and luminescent properties that allow the combination of diagnostic and therapeutic purposes, thereby permitting, e.g., molecules to be tracked within cells. In this review, we discuss the anticancer and antibiotic properties of rhenium tri- and dicarbonyl complexes described in the last seven years, mainly in terms of their structural variations and in vitro efficacy. Given the abundant literature available, the focus is initially directed on tricarbonyl complexes of rhenium. Dicarbonyl species of the metal ion, which are slowly gaining momentum, are discussed in the second part in terms of future perspective for the possible developments in the field.     

Pentafluorophenyl copper: aggregation and complexation phenomena, photoluminescence properties, and applications as reagent in organometallic synthesis

Recent advances in the chemistry of pentafluorophenyl copper are discussed, including the observation of strongly luminescent adducts with pyridine, the first successful structural characterization of an organocopper-arene complex, and the complexation with electron-rich transition metal complexes such as ferrocene derivatives. In addition, new applications in synthetic organometallic chemistry are discussed, which include the discovery of tin/copper exchange reactions for the preparation of organocopper compounds that are otherwise not readily accessible, and the selective transfer of the C(6)F(5) groups to boron to form catalytically active and electronically interesting organoboron polymers.     

Is Iron the New Ruthenium?

Ruthenium complexes with polypyridine ligands are very popular choices for applications in photophysics and photochemistry, for example, in lighting, sensing, solar cells, and photoredox catalysis. There is a long-standing interest in replacing ruthenium with iron because ruthenium is rare and expensive, whereas iron is comparatively abundant and cheap. However, it is very difficult to obtain iron complexes with an electronic structure similar to that of ruthenium(II) polypyridines. The latter typically have a long-lived excited state with pronounced charge-transfer character between the ruthenium metal and ligands. These metal-to-ligand charge-transfer (MLCT) excited states can be luminescent, with typical lifetimes in the range of 100 to 1000 ns, and the electrochemical properties are drastically altered during this time. These properties make ruthenium(II) polypyridine complexes so well suited for the abovementioned applications. In iron(II) complexes, the MLCT states can be deactivated extremely rapidly (ca. 50 fs) by energetically lower lying metal-centered excited states. Luminescence is then no longer emitted, and the MLCT lifetimes become much too short for most applications. Recently, there has been substantial progress on extending the lifetimes of MLCT states in iron(II) complexes, and the first examples of luminescent iron complexes have been reported. Interestingly, these are iron(III) complexes with a completely different electronic structure than that of commonly targeted iron(II) compounds, and this could mark the beginning of a paradigm change in research into photoactive earth-abundant metal complexes. After outlining some of the fundamental challenges, key strategies used so far to enhance the photophysical and photochemical properties of iron complexes are discussed and recent conceptual breakthroughs are highlighted in this invited Concept article.     

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.     

Expanded bite angles in tridentate ligands. Improving the photophysical properties in bistridentate RuII polypyridine complexes

Bistridentate metal complexes as photosensitizers are ideal building blocks in the construction of rod-like isomer-free assemblies for intramolecular photoinduced charge separation. Approaches to obtain long-lived luminescent metal-to-ligand charge transfer excited states in bistridentate Ru^II polypyridine complexes via the manipulation of metal-centered state energies are discussed. Following an introduction to general strategies to prolong the excited state lifetimes, more recent work is explored in detail where tridentate ligands with expanded 2,2′:6′,2″-terpyridine cores are utilized. The synthesis of these tridentate ligands and their corresponding Ru^II complexes is covered. Bistridentate Ru^II complexes with microsecond metal-to-ligand charge transfer excited state lifetimes are described, and are used in electron donor–photosensitizer–electron acceptor assemblies for efficient vectorial photoinduced charge separation.     

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.     

Syntheses and Structures of Blue Luminescent Zinc(Ⅱ) Complexes with 2,6-Bis(imino)pyridyl Ligands

Luminescent coordination compounds with nitrogen-containing ligands have attracted much attention due to their good performance in sensor and electroluminescent device techniques[1-17]. To develop new luminescent materials, a large number of d10 metal complexes, especially zinc complexes, with the nitrogen-containing ligands have been synthesized and their luminescence behaviour have been studied[1-11]. It has been found that for a given complex, the size of the π-conjugated system of the ligand and the electronic effect of substituents at the ligand are important factors for modulating its luminescent properties[5,8,9].     

Synthesis and Photophysical Properties of Novel Red Light-Emitting Cyclometalated Iridium(Ⅲ) Complexes

Considerable research is currently focused on the organic electrophosphorescent materials due to their high luminescent efficiency. Electrophosphorescent material based on heavy metal complexes is a hot topic in the research of organic light-emitting devices (OLEDs). We synthesized a series of novel cyclometalated heavy metal complexes by introducing pheny-quinoline moieties into ligands by means of a convenient method (Scheme 1), and investigated their photophysical properties which indicated that those compounds exhibited red light-emitting and high luminescent efficiency.These complexes have been characterized by 1H NMR, UV-vis and PL.     

发光ZnSalen配合物在分子荧光成像中的应用进展

荧光分子探针的设计、合成以及应用是分子荧光成像领域重要的化学问题.本文从Znsalen配合物的基本性质出发,概述了Znsalen配合物结构与功能的关系,特别是其发光性质与分子结构及分子聚集状态的相关性及应用.针对Znsalen配合物的发光性质,展示了其应用于分子荧光成像和活细胞中分子事件监测的研究进展.这些最新研究表明,Znsalen配合物探针的细胞毒性低(利于活细胞成像)、发光效率高(适用于单、双光子成像)、发光可调(通过配体的修饰和分子聚集状态的调节),有望作为一类重要的发光金属荧光探针实现在分子荧光成像中的应用.