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  • Iridium complexes with monodentate N-heterocyclic carbene ligands
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-27
    Gellért Sipos, Reto Dorta
    更新日期:2018-01-02
  • Nickel complexes as molecular catalysts for water splitting and CO2 reduction
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-28
    Jia-Wei Wang, Wen-Ju Liu, Di-Chang Zhong, Tong-Bu Lu
    更新日期:2017-12-31
  • Proton conductive metal phosphonate frameworks
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-28
    Song-Song Bao, George K.H. Shimizu, Li-Min Zheng

    This review covers basic design principles and offers a cross-section of the current status of phosphonate MOFs as proton conductors. Metal phosphonates are often sustained by strong bonds that render them very stable materials. The phosphonate group can also coordinate as a protonated species. These factors, coupled with the inherent structural versatility intrinsic to any metal organic framework family, are the foundation of their interest as proton conducting materials. This review summarizes the recent progress in this topical field as well as some of the existing challenges for further development. The present state of application of the materials is still largely in the academic domain but increasingly, new structures with the necessary proton conducting ability and stability to merit further development as membranes are being reported. The review concludes with a discussion of future challenges for development of this promising field.

    更新日期:2017-12-31
  • 更新日期:2017-12-27
  • 更新日期:2017-12-20
  • The photoluminescent metal nanoclusters with atomic precision
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-20
    Haizhu Yu, Bo Rao, Wan Jiang, Sha Yang, Manzhou Zhu

    Due to their ultrasmall size, low toxicity, strong photoluminescence and ease with which they can be chemically modified, luminescent metal (and especially the group IB metal) nanoclusters have attracted increasing research interest, and have emerged as one of the most attractive nanomaterials. Several methods, such as one-pot, ligand exchange, and metal exchange methods have been recently explored to synthesize atomically precise nanoclusters of various sizes and compositions; and the luminescence intensity of some of these is comparable to or even superior to that of the traditional fluorescent nanomaterials (such as quantum dots), and organic dyes. Specifically, their high photostability, purity and atomic precision provide an opportunity for an in-depth understanding into structure–optical property correlations. This review summarizes recent progress in the field, including synthetic protocols, structural characteristics, luminescence properties, and mechanistic investigations. The prospects for future development and applications are also covered.

    更新日期:2017-12-20
  • Labelling proteins and peptides with phosphorescent d6 transition metal complexes
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-19
    Timothy U. Connell, Paul S. Donnelly
    更新日期:2017-12-19
  • Kinetically-inert polypyridylruthenium(II) complexes as therapeutic agents
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-19
    Xin Li, Anil K. Gorle, Madhu K. Sundaraneedi, F. Richard Keene, J. Grant Collins
    更新日期:2017-12-19
  • Catalytic properties of chemical transformation within the confined pockets of Werner-type capsules
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-11
    Liang Zhao, Xu Jing, Xuezhao Li, Xiangyang Guo, Le Zeng, Cheng He, Chunying Duan

    The use of small molecules with defined cavities that catalyze unique chemical transformations to emulate enzyme sites have resulted in sustainable catalytic transformation with unprecedented selectivity that proceed under ambient conditions using benign solvents and clean energy. Of these reported host molecules, Werner-type capsules have been of particular interest to researchers because of their structural modifiability and rich chemical properties arising from their uniform cavities. In this review, we focus on the catalytic properties of several important catalytic transformations that have occurred within the confined pockets of these Werner-type capsules with special attention to the aspects that are derived from the ‘confined space effect’ of these Werner-type capsules.

    更新日期:2017-12-11
  • Reaction mechanisms of catalytic photochemical CO2 reduction using Re(I) and Ru(II) complexes
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-11
    Yusuke Kuramochi, Osamu Ishitani, Hitoshi Ishida

    Reduction of CO2 is one of the most important reactions that might solve the problems of global warming and shortage of fossil-fuel resources simultaneously. Metal complex catalysts are sometimes called molecular catalysts because they can be designed and synthesized on the molecular level. Some metal complexes are quite efficient and selective for CO2 reduction. Recently, such complexes have been applied as semiconductor photocatalysts to yield hybrid metal complex/semiconductor systems. Compared to heterogeneous catalysts, metal complexes are more advantageous for elucidating reaction mechanisms. This review summarizes the reaction mechanisms that have been proposed for the photochemical CO2 reduction reaction catalyzed by rhenium and ruthenium complexes. Rhenium complexes efficiently reduce CO2 to selectively produce CO under various reaction conditions. On the other hand, ruthenium complexes yield CO and HCOOH, and the product selectivities are strongly dependent on the reaction conditions. Numerous reaction mechanisms have been proposed; however, no universal mechanism that can completely explain the activities and product selectivities of these catalysts exists. Why are two important intermediates, the η1-CO2 adduct and the hydride complex, proposed? How does the η1-CO2 adduct produce HCOOH? Does the hydride complex yield CO via the formate complex? What is the second electron source for the intermediate that produces CO and HCOOH? This review highlights what is already known about photocatalytic CO2 reduction reaction mechanisms and what remains to be clarified.

    更新日期:2017-12-11
  • Switchable cobalt coordination polymers: Spin crossover and valence tautomerism
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-11
    Olga Drath, Colette Boskovic

    Electronically labile, or switchable, cobalt coordination polymers exhibit reversible spin crossover (SCO) or valence tautomeric (VT) transitions upon the application of an external stimulus, such as temperature variation. Spin crossover transitions at pseudo-octahedral cobalt(II) centers with an appropriate ligand field involve a heating-induced transition from the low-spin to high-spin electronic configurations. Valence tautomeric transitions are most commonly observed for cobalt-dioxolene systems, which undergo an intramolecular electron transfer and concomitant spin transition at the cobalt center, from low-spin-cobalt(III)-catecholate at low temperature to high-spin-cobalt(II)-semiquinonate upon heating. The VT transition can also be induced by light, while the cobalt(II) SCO transition cannot. Incorporation of these switchable moieties into coordination polymers (CPs) is generally achieved using polytopic nitrogen-donor linking ligands. All but one of the switchable cobalt CPs that have been structurally characterized are 1D chains, most of which exhibit VT transitions rather than SCO. There is a single example of a switchable 2D cobalt CP where VT cobalt-dioxolene moieties are linked by a tetratopic nitrogen-donor bridging ligand. Efforts to confer the VT properties to compounds suitable for applications as materials or in devices have mainly focused on the incorporation of the 1D chain VT CPs into nano- and microparticles, in which the VT transition is generally maintained. Valence tautomeric nanoparticles synthesized from 1D chain CPs have been grafted on to gold surfaces as self-assembled monolayers.

    更新日期:2017-12-11
  • Recent developments in the metallo-supramolecular chemistry of oligo-β-diketonato ligands
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-11
    Aidan J. Block, Jack K. Clegg, Feng Li, Leonard F. Lindoy

    Classical β-diketone ligands have been well demonstrated to exhibit a rich metal coordination chemistry yielding metal complexes displaying a variety of properties. The investigation of polydentate ligand derivatives containing more than one β-diketone domain, and in many instances also incorporating additional donor sites, have been demonstrated to react with a range of metal ion types to yield a wide range of metallo-supramolecular topologies. These include metallocyclic platforms, triangles, squares, cubes, helicates, tetrahedrons as well as other intricate structures that include a universal 3-ravel. In this report we cover the published literature in the area from 2008 with emphasis on the synthetic strategies employed as well as on the diverse structures of the metallo-supramolecular products obtained.

    更新日期:2017-12-11
  • Bright lights down under: Metal ion complexes turning the spotlight on metabolic processes at the cellular level ☆
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-08
    Todd A. Gillam, Martin J. Sweetman, Christie A. Bader, Janna L. Morrison, John D. Hayball, Doug A. Brooks, Sally E. Plush

    The widespread uptake and use of emissive metal ion complexes for investigating cellular structure, composition and function, is evidence of the effectiveness and vast potential for this type of imaging probe. Metal ion complexes provide significant advantages over their organic fluorophore counterparts, including long emission lifetime, resistance to photobleaching and the capacity to readily modify their peripheral chemistry to target specific organelles, signalling pathways and individual molecules. This review will discuss recent progress in the development and use of metal ion complexes, specifically for studying metabolic diseases at the cellular level. Advanced metal ion complexes for organelle imaging and the detection of biorelevant species, to elaborate complexes for understanding cellular mechanisms and recent therapeutic applications will be reviewed. To align with the special issue, Coordination Chemistry Reviews: Coordination Chemistry in Australia, the work of Australian researchers actively engaged in this field is featured prominently, along with key developments from the global research community.

    更新日期:2017-12-10
  • Lanthanoid tetrazole coordination complexes
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-07
    Massimiliano Massi, Stefano Stagni, Mark I. Ogden

    While tetrazole derivatives are well established as anionic ligands for d-block elements, there is a growing interest in lanthanoid complexes of these compounds. Diverse structural chemistry results from the presence of four potential donor N atoms, and the conjugated nature of the heterocycle can impact on the photophysical properties of the complexes. This review examines the range of structurally characterised lanthanoid–tetrazolato complexes, focussing on the structural features of the ligand that impact on the tendency to interact with the first or second coordination spheres.

    更新日期:2017-12-07
  • Recent advances in post-synthetic modification of metal–organic frameworks: New types and tandem reactions
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-06
    Zheng Yin, Shuang Wan, Jian Yang, Mohamedally Kurmoo, Ming-Hua Zeng

    In the past five years, post-synthetic modification (PSM) has become a very useful strategy in systematically functionalizing metal–organic frameworks (MOFs) by modifying the linker, metal node, pore character, and surface environment for the purpose of increasing the structural stability and introducing desired properties. In this review, we intend to demonstrate the two major trends in PSM including the mushrooming of new types of reaction and the combination of multi-steps PSM. The selected examples illustrate three promising PSM classes, post-synthetic metal exchange (PSME), post-synthetic ligand exchange (PSLE) and post-synthetic elimination and insertion (PSE&I). Combined with the well-developed covalent PSM and dative PSM, tandem PSM which constitutes of multistep and different types of reaction adds to the step-by-step improvement of catalytic activity, regulating magnetism and others. These recent advances in PSM not only open new paths to improve the function of MOFs, but also reveal the unprecedented reaction complexity of crystalline solids.

    更新日期:2017-12-06
  • Redox-coupled structural changes in copper chemistry: Implications for atom transfer catalysis
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-06
    Timothy J. Zerk, Paul V. Bernhardt

    The coordination chemistry of copper is dominated by its monovalent and divalent oxidation states and interplay between the two is central to the role of copper-based homogeneous catalysts. Upon reduction of most copper(II) complexes, which commonly are five coordinate, the coordination number rapidly changes to four or less. This feature is advantageous for atom transfer reactions where single electron transfer is coupled to the association or dissociation of a radical. Although this coupled change in coordination number and oxidation state is central to the mechanism of atom transfer reactions, its importance to catalysis is not widely appreciated. Herein we review the structural chemistry of copper(I) and copper(II) with a range of multidentate N-donor ligands employed in atom transfer radical polymerisation (ATRP). The remarkable resistance of copper(I) to accept more than four donor atoms is illustrated and discussed in the context of both its solid state and solution structures.

    更新日期:2017-12-06
  • Luminescent single-molecule magnets based on lanthanides: Design strategies, recent advances and magneto-luminescent studies
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-06
    Jian-Hua Jia, Quan-Wen Li, Yan-Cong Chen, Jun-Liang Liu, Ming-Liang Tong

    Incorporation of two characters into one molecular entity is an effective way to afford bifunctional molecule-based materials. Lanthanides serve as a group of preferable objectives for the construction of luminescent single-molecule magnets (SMMs) due to their excellent performances in areas of SMM and luminescence for molecular materials, showing a great potential of applications in high-density data storage, quantum computing, light-emitting diodes, biofluorescence labelling, etc. This review concentrates on the design strategies for the construction of luminescent SMMs referring to the organic chromophores and transition metal-containing chromophores as the antennas, as well as the recent examples of luminescent SMMs. To investigate the magneto-luminescent behavior (including the magneto-luminescent coupling), a few of classical complexes are discussed in the review to emphasize the importance of studying the correlation/coupling between relaxation mechanism and luminescence for lanthanide SMMs.

    更新日期:2017-12-06
  • Metal–organic frameworks and porous organic polymers for sustainable fixation of carbon dioxide into cyclic carbonates
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-06
    Jun Liang, Yuan-Biao Huang, Rong Cao

    The capture and chemical fixation of carbon dioxide (CO2) into cyclic carbonates is considered to be a promising way to alleviate CO2 concerns and produce fine chemicals. This process can be effectively promoted by various kinds of newly developed porous heterogeneous catalysts with Lewis acidic and nucleophilic sites. These porous catalytic materials include metal–organic frameworks (MOFs), covalent-organic frameworks (COFs), nanoporous ionic organic networks (NIONs) and amorphous porous organic polymers. In this review, we have briefly classified these materials based on their different structural features and compositions. The syntheses and catalytic performances of these porous heterogeneous catalysts are described from the perspective of catalyst design. This review will guide material scientists attempting to design more efficient porous catalysts for CO2 capture and conversions.

    更新日期:2017-12-06
  • Lanthanide complexes for luminescence-based sensing of low molecular weight analytes
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-06
    Margaret L. Aulsebrook, Bim Graham, Michael R. Grace, Kellie L. Tuck

    Recent developments (2012 and onwards) in the design and application of luminescent lanthanide-based complexes for chemical sensing are reviewed. Sensors for a variety of metal cations, anions and neutral small molecules are highlighted, including several developed by Australian researchers. Emphasis is placed on describing the general design features and range of mechanisms by which such sensors are able to elicit a luminescent response upon exposure to an analyte.

    更新日期:2017-12-06
  • Harnessing the properties of cobalt coordination complexes for biological application
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-06
    Anna K. Renfrew, Edward S. O'Neill, Trevor W. Hambley, Elizabeth J. New

    Cobalt is an essential metal that is found in very low abundance in the body and the environment. Cobalt coordination complexes exhibit interesting redox and magnetic properties that make them suitable for a remarkable breadth of applications in biology and medicine. Here we review the diversity of uses of cobalt complexes in imaging and therapy, and highlight the most promising directions for future research.

    更新日期:2017-12-06
  • Recent progress for reversible homogeneous catalytic hydrogen storage in formic acid and in methanol
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-01
    Naoya Onishi, Gábor Laurenczy, Matthias Beller, Yuichiro Himeda

    Development of technologies using hydrogen as an energy carrier instead of fossil fuels is strongly required today. Especially, new, reversible, sustainable hydrogen storage technologies have received increasing attention. Formic acid (FA) and methanol (CH3OH) are considered as effective liquid chemicals for hydrogen storage as being easier to handle than solid or gas materials. This review summarizes the recent progress of research on the development of homogeneous catalysts mainly focusing on FA and CH3OH and the reports on the complexes based on both precious and non-precious metals which are rapidly increasing in the past few years.

    更新日期:2017-12-02
  • Platinum coordination compounds with potent anticancer activity
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-12-01
    Krishant M. Deo, Dale L. Ang, Brondwyn McGhie, Adeline Rajamanickam, Ankita Dhiman, Aleen Khoury, Jason Holland, Aleksandra Bjelosevic, Benjamin Pages, Christopher Gordon, Janice R. Aldrich-Wright

    Many international researchers have strived to understand the mechanism of action or improve the efficacy of inorganic coordination compounds that have been identified to exhibit anticancer activity. The inherent challenges of chemotherapy demand that new strategies be developed utilising different mechanisms of action to interrupt the cellular machinery of cancer cells. In Australia, we have benefited from the research of colleagues who have influenced modern platinum chemistry by contributing to our understanding of platinum oxidation and reduction, the mechanism of action of cisplatin, and unique design strategies for new platinum complexes. It was our goal with this review to provide some background in the history and development of platinum(II) and platinum(IV) complexes.

    更新日期:2017-12-02
  • Transition metal-induced B–H functionalization of o-carborane
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-24
    Xiaolei Zhang, Hong Yan

    Transition metal-mediated B–H functionalization of carboranes has drawn increasing interests during the last two decades. This review describes how to incorporate B–H functionalization into the derivation of half-sandwich transition metal complexes containing o-carborane dichalcogenolates. The detailed mechanistic elucidations for metal-induced versatile B–H functionalization are also reviewed. Examples of selective B–H activation, stepwise B–H functionalization, cobalt-mediated B–H functionalization as well as dimetal-mediated B–H activation of o-carborane are discussed.

    更新日期:2017-11-24
  • Bipyridinium derivative-based coordination polymers: From synthesis to materials applications
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-22
    Jian-Ke Sun, Xiao-Dong Yang, Guo-Yu Yang, Jie Zhang

    The past decade has witnessed the rapid development of functional coordination polymers (CPs) for various potential applications. Generally speaking, functionalization of coordination framework to enhance materials performance could be achieved either during the framework formation or by post-synthesis modification. In spite of great progress over the past few years, there is still growing demand in expanding the research by introducing new structure motifs, among which the incorporation of stimuli-responsive ligand into the coordination skeleton is an option. In particular, the fusion of typically charged units, e.g. bipyridinium derivatives with metal ions to fabricate CPs has attracted tremendous attention. The electrostatic interaction, electron-deficient characteristic and photoelectrochemical activity make this family of materials show a wide variety of intriguing applications including smart chromic response, switching, sensing, adsorption and separation, and molecular magnets, etc. This review aims to highlight the recent progress in this area, and seek to uncover promising ideas that will stimulate future advancements at both the basic and applied levels.

    更新日期:2017-11-22
  • Recent advances in alkoxylation chemistry of polyoxometalates: From synthetic strategies, structural overviews to functional applications ☆
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-22
    Jiangwei Zhang, Yichao Huang, Gao Li, Yongge Wei

    Polyoxometalates (POMs), an exceptional family of coordination clusters consisting of Mo, W, V, etc. early transition metal ions in their highest oxidation states, have received significant attention over recent years due to their structural versatility and unique and diverse chemical and physical properties. The functionalization of POMs with organic ligands provides a novel strategy to precisely incorporate POMs with advanced functional organic moieties on their surfaces and enhance their compatibility in organic media. Among the various organically functionalized synthetic strategies for POM-based organic–inorganic hybrid materials, alkoxylation of POMs stands for one of the hottest topics during the past decades, since the diverse and tunable alkoxyl ligands are able to anchor on the surface of many POMs clusters, forming novel and flexible organically functionalized POM clusters, which can be further exploited as building blocks to design various functionalized POM-based hybrids with charming catalytic properties, and biomedicine, energy, or functional materials applications. In this review, recent advances in alkoxylation chemistry of POMs from synthetic strategies, structural overviews to their functional applications have been discussed.

    更新日期:2017-11-22
  • Primary and secondary directing interactions of aquated lanthanide(III) ions with p-sulfonated calix[n]arene
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-21
    Irene Ling, Colin L. Raston

    This review reports on the solid-state structural analysis of primary and secondary coordination interactions between aquated lanthanide(III) ions and p-sulfonatocalix[n]arenes. These different interactions control the nature of the overall packing motif of the two components in the solid-state, with a diverse range of structures accessible. Structures with higher complexity can form in ternary systems, incorporating either or both endo- and exo-calixarene cavity guest molecules.

    更新日期:2017-11-22
  • Molecular/polymeric metallaynes and related molecules: Solar cell materials and devices
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-21
    Linli Xu, Cheuk-Lam Ho, Li Liu, Wai-Yeung Wong

    Energy remains one of the great challenges for the world. There is a considerable interest in developing renewable energy resources and improving the technologies for energy conversion. In this context, solar energy is a source with the proven capacity to meet the increasing global energy needs. In recent years, efficient organic solar cells (OSCs) have been fabricated using organic polymers and small molecules. Metalated conjugated organic molecules have also been shown to be good alternatives to the all-organic congeners and have demonstrated good promise as solar cell materials in OSCs and dye-sensitized solar cells (DSSCs). Among these, soluble molecular/polymeric metallaynes and their acetylide-functionalized metalloporphyrins show promising results in much of these investigations with the best power conversion efficiencies of 9.06% (for single-layer OSC), 12.5% (for tandem OSC) and 13.2% (for co-sensitized DSSC) to date. This review summarizes the recent advances of this field. Various factors influencing the device performance such as the nature of metal center and organic spacer, absorption coefficient, bandgap energy, charge carrier mobility, accessibility of triplet excitons and blend film morphology of these materials will be discussed. Given the diversity of transition metals available (for example, Pt, Zn, Ru) and structural versatility of the organic components, it is anticipated that this nascent field using metalated organic materials would continue to lead to exciting prospects in the near future.

    更新日期:2017-11-22
  • Molecular magnetism of lanthanide: Advances and perspectives
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-20
    Zhenhua Zhu, Mei Guo, Xiao-Lei Li, Jinkui Tang

    The discovery of the first example of lanthanide-based single molecule magnets (Ln-SMMs), a revolutionary progress, marked the beginning of a new age for SMMs, has greatly inspired researchers to invest their efforts in the design of high-performance SMMs by introducing lanthanide ions, especially dysprosium ions. Lanthanide ions have always been considered as excellent candidates to construct single-molecule magnets for high-density data storage and quantum calculation. Impressive progress has been made in field of Ln-SMMs where synthetic chemists have played a major role through producing suitable systems for detailed study by physicists and materials scientists. In this review, some recent breakthroughs changing the perspective of the field will be highlighted with special emphasis on the synthetic efforts made in this fascinating and challenging field. Their findings on the elucidation of relaxation dynamics and the synthetic strategies towards high-performance Ln-SMMs provide valuable insights required to optimize the contribution of an Ising type spin to a molecular magnet and indicate the directions to which further synthetic efforts should be focused.

    更新日期:2017-11-20
  • Europium-activated luminescent nanoprobes: From fundamentals to bioapplications
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-20
    Datao Tu, Wei Zheng, Ping Huang, Xueyuan Chen

    Trivalent europium ions (Eu3+) activated inorganic materials, known as one of the most important red-emitting phosphors, are emerging as an attractive class of luminescent materials over the past decades. Specifically, Eu3+ ion is considered as an ideal spectroscopic probe to decipher the local environment in view of its non-degenerate ground state of 7F0 and excitation state of 5D0. Benefiting from the intense long-lived luminescence from 5D0, Eu3+-activated inorganic nanoparticles are also frequently reported as luminescent probes in biological assays and medical imaging. With the development of advanced synthesis strategies and characterization techniques, more new understanding or progress in Eu3+-activated luminescent nanoprobes have been gained with regard to their fundamental photophysics/photochemistry properties and versatile bioapplications. As such, it is urgent to renew the knowledge in this field. Rather than being exhaustive, this review aims to highlight the latest progress in the electronic structures, optical properties and emerging bioapplications of Eu3+-activated nanoprobes, which covers from spectroscopic site symmetry, excited-state dynamics, downshifting/upconversion luminescence enhancement strategies, and luminescent biosensing, with an emphasis on their heterogeneous/homogeneous biodetection as well as in vitro and in vivo bioimaging. Some future prospects and efforts toward this rapidly developing field are also discussed.

    更新日期:2017-11-20
  • Metallosalen-based crystalline porous materials: Synthesis and property
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-20
    Guozan Yuan, Hong Jiang, Liyan Zhang, Yan Liu, Yong Cui

    Salen-type ligands have been used extensively to stabilize metals for homogeneous catalysis. It has been demonstrated that the marriage of complexes of salen with porous materials is a promising way to combine the attractive properties of the salen complexes with those of the porous structures. In this review, we summarize the recent research progress in metallosalen-based crystalline porous materials (CPMs), including metal–organic frameworks, coordination metallacycles, and covalent organic frameworks. Emphasis is placed on the syntheses, and structures of these porous materials, and their properties of catalysis, molecule separation, sensing and magnetic resonance imaging.

    更新日期:2017-11-20
  • Homo and heterometallic gold(I) clusters with hypercoordinated carbon
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-20
    Zhen Lei, Quan-Ming Wang

    Gold clusters have attracted great interest for a long time, and homo and heterometallic gold clusters with hypercoordinated carbon are particularly interesting. This is due to their novel structures and intriguing physicochemical properties. In this review, recent results concerning homo and heterometallic gold(I) cluster compounds with hypercoordinated carbon are summarized, with emphasis on the rational design of phosphine ligands, synthesis of clusters, structure analysis, photophysical studies and their applications such as light emitters, cellular dyes and chirality sensors. We demonstrate that ligand modification, coordination of secondary metal ions and post-clustering functionalization are useful approaches in the preparation of carbon-centered homo and heterometallic gold clusters. The chemical stability of the cluster is enhanced through the binding between the hypercoordinated carbon and gold atoms. These gold clusters exhibit strong luminescence and are useful in cell imaging and chiral sensing. In addition, combine with ultrafast absorption experiments and quantum chemical calculations, the relationship between structures and properties of carbon-centered homo and heterometallic gold(I) clusters has been revealed.

    更新日期:2017-11-20
  • Chiral metal–organic cages/containers (MOCs): From structural and stereochemical design to applications
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-20
    Mei Pan, Kai Wu, Jian-Hua Zhang, Cheng-Yong Su

    During the past few decades, great efforts have been devoted to the design and self-assembly of discrete metal–organic cages/containers (MOCs) with increasing complexity and functionality. Among which, the incorporation of chirality into the construction of MOCs endows these supramolecular containers with unique potentials in stereochemical, nonlinear optical, biomedical and enzyme mimical fields. In this review, we give a brief survey of recent works focusing on the assembly and applications of chiral metal–organic convex polyhedra with well-defined three-dimensional (3D) outer shapes and inner cavities, including a few examples of chiral MOCs in other configurations. In general, the stereochemical origin of a chiral MOC can be generated through geometrical symmetry control pathways by removing the inherent inversion and/or mirror symmetries, in which the vertice-, edge-, and face-directed assembling approaches represent the most successful strategies to introduce stereogenic centers into and achieve absolute chiral environments in MOCs. Stereochemical memory, transfer and communication can be realized among different components of chiral MOCs in a supramolecular sense, resulting in cooperative and synergetic effects of chiral complex systems, which can be further explored for enantio-recognition, separation and asymmetric catalysis applications.

    更新日期:2017-11-20
  • Dinuclear N-heterocyclic carbene copper(I) complexes
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-15
    Michael Trose, Fady Nahra, Catherine S.J. Cazin

    Copper(I) species exhibit various coordination modes as a function of surrounding ligands. Complexes bearing N-heterocyclic carbenes as ligands are usually monomeric species with the copper adopting a linear geometry. Contrarily to the parent phosphine complexes, in which the presence of species of higher nuclearity is well established, fewer examples of such copper(I)–NHC species are reported and, interestingly, their number is growing. Moreover, these are no longer a mere curiosity from a coordination perspective since they have been shown successful in catalysis. The aim of this review is to present a summary of the synthesis and structural properties of dinuclear copper(I)–NHC complexes. It is our hope that by centralizing all information available on such species, future efforts aimed at exploiting their full potential can be facilitated.

    更新日期:2017-11-17
  • Amide-functionalized metal–organic frameworks: Syntheses, structures and improved gas storage and separation properties
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-13
    Dong-Xu Xue, Qian Wang, Junfeng Bai

    Metal–organic frameworks (MOFs) emerging as a new type of solid state porous materials have received intensive attentions in academia and industry for the last two decades. MOF materials demonstrate not only intriguing structures/topologies, but also a variety of functionalities/applications, i.e. mediating the currently on demanding energy crisis and environmental pollution. We are interested in design and self-assembly of functional MOF materials to improve the carbon dioxide, hydrogen, methane and acetylene storage capabilities, as well as the separation efficiencies toward flue gas and nature gas. Therefore, significant efforts have been devoted to construct a subclass of called amide-functionalized metal–organic frameworks (AFMOFs) in the last decade in our research group to target the above-mentioned applications. Due to the intrinsic nature, i.e. flexibility and polarizability of amide groups, the resultant AFMOFs unveil a myriad of graceful structures/topologies in combination with enhanced gas storage and separation properties. Depending where the amide groups are implanted into organic backbones, two types of AFMOFs were essentially afforded in our research group. In this review, we first pay less attention on the synthesis and structures of dynamic AFMOFs, in which the amide groups are built between carboxymethyl and phenyl rings. Then, we discuss the designs, syntheses and constructions of robust AFMOFs by means of several intriguingly topological platforms, i.e. pcu-, agw-, nbo-, rht-, pbz- and txt-MOFs, where the amide groups are built between phenyl and phenyl rings. Later, several outstanding AFMOFs are chosen to elucidate their applications for energy gas storage and carbon capture as well as acetylene safe handling.

    更新日期:2017-11-14
  • Goal-directed design of metal–organic frameworks for liquid-phase adsorption and separation
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-13
    Qi Zhang, Yuanjing Cui, Guodong Qian

    Metal–organic frameworks (MOFs) which are constructed from metal ions/clusters with organic linkers are in a stage from fundamentals to applications. The application of MOFs in liquid-phase adsorption/separation is one of the most significant headway in environment and chemistry. Concerning tunable porosity, multiple functional sites and devisable host–guest interactions, goal-directed designs lead to task-specific MOFs and are requisite to perform precise molecular recognition in liquid-phase adsorption/separation. In this review, we give insights into the goal-directed design strategies of organic linkers and metal clusters for the elaboration of task-specific MOFs with targeting effect and high recognition capability, as well as related progress of MOF-derived membranes. In addition, we put forward the cooperation of different recognition mechanisms to achieve high adsorption/separation performance. At the end, we address the challenges in these fields and propose the prospects and possible evolution for future development.

    更新日期:2017-11-13
  • Recent advances in the assembly of high-nuclearity lanthanide clusters
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-11
    Xiu-Ying Zheng, Jing Xie, Xiang-Jian Kong, La-Sheng Long, Lan-Sun Zheng

    High-nuclearity lanthanide clusters have attracted much attention in different fields because of their unique physical and chemical properties and their potential applications. In this review, the synthetic strategy and building blocks for the assembly of high-nuclearity lanthanide clusters are outlined based on recently reported high-nuclearity lanthanide clusters. Perspectives for future studies on high-nuclearity lanthanide clusters are also discussed. We hope this review will provide insight into future research on high-nuclearity lanthanide clusters.

    更新日期:2017-11-11
  • Recent progress in organohalide lead perovskites for photovoltaic and optoelectronic applications
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-11
    Abd Rashid Bin Mohd Yusoff, Peng Gao, Mohammad Khaja Nazeeruddin

    Perovskite solar cells (PSC) based on organic–inorganic materials are considered to be the most promising photovoltaic technology because of their meteoritic progress in power conversion efficiency (PCE) from 3.8% to 22% to address the increasing energy demand, greenhouse gasses, and depleting fossil fuels. The breakthrough regarding the device efficiency and reproducibility is a combination of compositional engineering of cations, anions, the presence of a non-stoichiometric excess of lead iodide, and solvent engineering to grow over-layer of perovskite on top of the mesoporous layer. The last few years have witnessed a breakthrough in mixed-halide perovskite solar cells where the perovskite layer sandwiched in between selective charge extracting materials for the highly efficient solar cells. However, guidelines for interface engineering, essential for photovoltaic and optoelectronic applications, are still missing. This review will derive rationale understanding for future device development, revealing the exact interfacial processes for photovoltaic and optoelectronic Applications and their perspectives.

    更新日期:2017-11-11
  • Molecular catalysts of Co, Ni, Fe, and Mo for hydrogen generation in artificial photosynthetic systems
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-10
    William T. Eckenhoff

    Driven by population and quality of living increases, the global consumption of energy is expected to dramatically increase over the course of the century. To avoid meeting this demand with fossil fuels, new carbon neutral energy sources must be implemented which are competitive in cost and performance with those currently in use. Hydrogen is a possible candidate to meet this need but carbon-free production of hydrogen needs to be developed. This chapter specifically examines the progress of homogeneous catalysts used in hydrogen production via artificial photosynthesis. Only those catalysts based on earth abundant metals, such as Co, Ni, Fe, and Mo are discussed as inexpensive mass production would require such materials, as opposed to expensive and rare metals, such as Pt, Pd and Rh. Electrocatalytic studies are also discussed as it pertains to the light driven systems and mechanistic insights.

    更新日期:2017-11-11
  • Weiss’ Reagents: A synthetically useful class of iodine(III) coordination compounds
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-06
    Robert Corbo, Jason L. Dutton

    The growing use of pyridine stabilized polycationic I(III) regents ([PhI(Pyr)2]2+) as versatile oxidizing agents is reviewed. Currently the number of examples describing the use of these oxidants is modest, however those that do exist are spread across a diverse range of topic areas. The highly oxidizing nature of the [PhI(Pyr)2]2+ polycations coupled with the potential for neutral ligand delivery to metal centers or in situ generation of the reactive [PhI]+ electrophile gives access to a range of novel transformations across topic areas including organic, heavy main-group centered and organometallic chemistry.

    更新日期:2017-11-10
  • Understanding the polychalcogenides as building blocks to solid state materials: Speciation of polychalcogenides in solutions
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-06
    Peter K. Dorhout, Nichole B. Ford, Casey C. Raymond

    Many chalcogenide compounds are formed from a diverse set of primary building blocks that include binary salts of alkali metal chalcogenides that are reacted with metals or metal salts in a variety of solutions and reaction conditions to form highly-diverse structures with varying and interesting physical properties. This review expands upon an earlier review by our group in 1997 that incorporates many of the more recent studies on the speciation of polysulfides, polyselenides, and polytellurides in aqueous and non-aqueous solutions and what has been learned in the intervening 20 years. We introduce comparisons of solution speciation across different spectroscopic platforms and provide further evidence for the use of electrospray mass spectrometry, in conjunction with complementary techniques that offer a glimpse of possible reaction compositions that lead to new materials.

    更新日期:2017-11-10
  • Organelle-targeting metal complexes: From molecular design to bio-applications
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-11-06
    Kangqiang Qiu, Yu Chen, Thomas W. Rees, Liangnian Ji, Hui Chao

    Cellular organelles, such the cytomembrane, lysosome, mitochondrion, Golgi apparatus, the endoplasmic reticulum, and nucleus, play important roles in the normal function of cells. Organelle-targeting bioimaging can aid our understanding of how organelles function, while the development of organelle-targeting therapy could deliver treatment for a variety of diseases. Possessing important advantages such as their photophysical properties, cytotoxicity, and cellular uptake mechanisms, metal complexes for organelle-targeting bio-applications have attracted increasing attention in recent years. In this review, organelle-targeting regulating strategies, and the characteristics of organelle-targeting metal complexes as well as their bio-applications are summarized. Moreover, the existing opportunities/challenges of organelle targeting are outlined and emphasized to inspire the design of a new generation of organelle-targeting metal complexes.

    更新日期:2017-11-10
  • 更新日期:2017-11-01
  • Heterogeneous catalysts based on mesoporous metal–organic frameworks
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-10-27
    Wenlong Xu, Kedar Bahadur Thapa, Qiang Ju, Zhenlan Fang, Wei Huang

    Mesoporous metal–organic frameworks (meso-MOFs) are emerging as promising functional materials for heterogeneous catalysis due to their high surface area, porosity, readily adjustable structures and tunable functionalities. Their properties and functions are often dictated by the size and shape of pores in their frameworks. Mesopores in MOFs can decline mass transfer and exchange resistance in a confined space, leading to the improvement of their catalytic performances. However, it is challenging to synthesize and apply meso-MOFs for catalysis owing to the requirement of a combination of good chemical stability and large pore size. So far, there have been few efforts to comprehensively discuss these issues. Based on selected recent reports, this review will provide a concise overview in the field of meso-MOFs, associated with their synthetic strategies and intriguing tactics of generating active sites for heterogeneous catalysis.

    更新日期:2017-10-27
  • 更新日期:2017-10-27
  • Stimuli responsive phthalocyanine-based fluorescent probes and photosensitizers
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-10-26
    Roy C.H. Wong, Pui-Chi Lo, Dennis K.P. Ng
    更新日期:2017-10-27
  • Photosensitization and controlled photosensitization with BODIPY dyes
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-10-26
    Abdurrahman Turksoy, Deniz Yildiz, Engin U. Akkaya

    Highly versatile BODIPY dyes proved themselves to be very useful as photosensitizers. These dyes can be derivatized to absorb essentially anywhere in the visible the near IR region of the spectrum. As a result of their diverse reactivity, singlet oxygen generation efficiency can be modulated very precisely, leading to a number of selective photosensitizers for photodynamic therapy. Among the biologically relevant modulators, glutathione concentration and pH received particular attention. In this review, we highlight modulatable BODIPY-based photodynamic photosensitizers, and various synthetically useful chemical reactions triggered by singlet oxygen and other reactive oxygen species generated by BODIPY-based photosensitizers.

    更新日期:2017-10-26
  • Sustainable metal complexes for organic light-emitting diodes (OLEDs)
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-10-24
    Claudia Bizzarri, Eduard Spuling, Daniel M. Knoll, Daniel Volz, Stefan Bräse

    Organic light-emitting diodes (OLEDs) produced from metal complexes play an important role in modern electroluminescent devices. While OLEDs are being used in display various applications such as TVs, smartphones and wearables already, a drastic increase in the production volume in the next years is being expected as soon as OLED lighting applications and printed OLEDs hit the market. Given that thus far, phosphorescent iridium compounds are required to make these products, sustainability issues are imminent. To review viable alternatives, we highlight the current status of sustainable metal complexes with a special focus on copper and zinc complexes. Ligand structures and complex preparation were highlighted. We also briefly address features like cooperativity, chirality, and printing.

    更新日期:2017-10-24
  • Nanoscale metal–organic frameworks for phototherapy of cancer
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-10-21
    Guangxu Lan, Kaiyuan Ni, Wenbin Lin
    更新日期:2017-10-21
  • 更新日期:2017-10-20
  • Porous metal–organic frameworks for fuel storage
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-10-16
    Yabing He, Fengli Chen, Bin Li, Guodong Qian, Wei Zhou, Banglin Chen
    更新日期:2017-10-16
  • d10 coinage metal organic chalcogenolates: From oligomers to coordination polymers
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-10-12
    Oleksandra Veselska, Aude Demessence
    更新日期:2017-10-13
  • Texaphyrin: From molecule to nanoparticle
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-10-10
    Joseph M. Keca, Gang Zheng

    In the present review, we present the history and future of texaphyrins, pentaaza Schiff base macrocycles with an expanded 5-coordination sphere, possessing chelation prowess of 24 different stable 1:1 complexes. Intrinsically unique photophysical and magnetic properties of metallotexaphyrins have enabled a broad spectrum of applications, resulting in multiple clinical phase trial evaluations of these compounds. The combination of texaphyrins with nanotechnology underscores the promising future of these materials, which aims to resolve inherent limitations of molecular counterparts in a nanovehicle.

    更新日期:2017-10-11
  • Exploration of porous metal–organic frameworks for gas separation and purification
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-10-09
    Rui-Biao Lin, Shengchang Xiang, Huabin Xing, Wei Zhou, Banglin Chen
    更新日期:2017-10-10
  • Structural systematics of some trinuclear alkynyl and diynyl Group 11 complexes containing dppm [dppm = CH2(PPh2)2]
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-10-09
    Michael I. Bruce, Jean-François Halet, Boris Le Guennic, Brian W. Skelton, Alexandre N. Sobolev, Christopher J. Sumby, Allan H. White

    In this review the molecular structures of a series of trinuclear alkynyl and diynyl Group 11 cations [{M3(μ-dppm)3}(X)n](3−n)+ (M = Cu, Ag; n = 1, 2; where X is an alkynyl or diynyl group, an inorganic anion or solvent) are considered from the points of view of (i) the dimensions and geometries of the M3(P–P)3 cores, (ii) the conformations of the dppm ligands, and (iii) the attachment of the alkynyl and diynyl ligands. In the crowded [M3(μ-dppm)3]3+ core, the dppm ligands are arranged so that there is always one CH2 group up and two down, to give pseudo mirror symmetry perpendicular to the M3 plane (crystallographic in some cases). Attachment of the alkynyl or diynyl substituent(s) occurs roughly normal to the M3 plane; according to their perpendicularity, the C(1) atom may be μ2 or μ3. In most cases where only one alkynyl or diynyl ligand is present, a second ligand is also attached to the M3 core. Unusual and interesting dispositions/conformations of the dppm ligands are widespread, among the mono–diynyl complexes in particular, whereby some phosphorus donor atoms lie at unusual distances out of the M3 planes, a concomitant of strong agostic interactions between phenyl H atoms and the atoms of the open M3 face, and weak M⋯M interactions. With one X group, C single bond H⋯M interactions persist on the other face, with C single bond H⋯X interactions with the alkyne affecting the inclination of the alkyne and the conformation of the Ph rings. With two substituents (one of which may be a loosely bound anion), similar interactions may occur, accompanied by twisting of the dppm chelate ring to displace P atoms from the M3 plane. These factors possibly inhibit formation of the bis(diyndiyl) complexes, which are only obtained under more strongly basic conditions.

    更新日期:2017-10-09
  • 更新日期:2017-10-06
  • Luminescent metal–organic frameworks and coordination polymers as alternative phosphors for energy efficient lighting devices
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-10-05
    William P. Lustig, Jing Li

    The development of lower cost and higher performance phosphor materials for energy efficient lighting and other optoelectronic applications is both necessary and feasible. Luminescent metal–organic frameworks and coordination polymers (LMOFs and LCPs, respectively) are a class of materials that hold great promise for this application. Their luminescence is eminently tunable, and a myriad of structures with incredibly diverse properties have been reported, with emission wavelengths covering the entire visible spectrum, white light emission from a variety of mechanisms, and quantum yields approaching unity. This review will briefly describe the luminescence mechanisms commonly observed in these materials, discuss strategies for the rational design of LMOF/LCP phosphors, and present a number of representative examples of each mechanism and/or design strategy.

    更新日期:2017-10-06
  • 更新日期:2017-10-06
  • 更新日期:2017-10-05
  • Structural phase transition-associated dielectric transition and ferroelectricity in coordination compounds
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-09-30
    Chao Shi, Xiang-Bin Han, Wen Zhang

    Structural phase transition in solid-state materials is an underlying factor for emergence and evolution of a number of important physical/chemical properties. In this review, we summarize recent achievements on two types of structural phase transition-associated properties, i.e., dielectric transition and ferroelectricity, in coordination compounds. The basic concepts and fundamentals of structural phase transition and the two properties are briefly introduced. This review aims to reveal the role of the structural phase transitions on bulk properties and afford a perspective on the connections among multiple topics of coordination chemistry from the structural phase transition viewpoint. It would be appealing to researchers in multidisciplinary fields such as coordination chemistry, crystal engineering, supramolecular chemistry, condensed matter physics, responsive materials and molecular machines.

    更新日期:2017-10-01
  • Upconversion-based photodynamic cancer therapy
    Coordin. Chem. Rev. (IF 13.324) Pub Date : 2017-09-30
    Yanyan Liu, Xianfu Meng, Wenbo Bu

    Photodynamic therapy (PDT) has become widely accepted and utilized for tumor therapy. Considering the natural shortcomings (e.g., lack of an ideal photosensitizer and limited light penetration depth), lanthanide doped upconversion nanoparticles (Ln-doped UCNP), which can be excited with near-infrared light (NIR) for UV/visible/NIR upconversion luminescence (UCL) emissions, show great potential for augmenting biological treatment with PDT for solid tumors and for visual bioimaging of disease lesions. This review summarizes the basic concepts and important influence factors on PDT, the optimized construction of UCNP-based photosensitizer (UCNP-PS) systems, and some representative examples of UCNP-based PDT (UC-PDT) applications in combination with other traditional therapy methods, such as chemotherapy, radiotherapy, photothermal therapy (PTT) and gene therapy. This review will provide guidance for the design and fabrication of future new UCNP-based nanocomposites for synergistic UC-PDT therapy.

    更新日期:2017-09-30
Some contents have been Reproduced with permission of the American Chemical Society.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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