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  • Goal-directed design of metal–organic frameworks for liquid-phase adsorption and separation
    Coordin. Chem. Rev. (IF 14.499) 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 headways in the 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 effects and high recognition capability, as well as the 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:2018-07-14
  • Amide-functionalized metal–organic frameworks: Syntheses, structures and improved gas storage and separation properties
    Coordin. Chem. Rev. (IF 14.499) 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 material, have received intensive attention in academia and industry over the last two decades. MOF materials demonstrate not only intriguing structures/topologies, but also a variety of functionalities/applications, i.e., mediating the currentdemanding energy crisis and environmental pollution. We are interested in the design and self-assembly of functional MOF materials to improve 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 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 on where the amide groups are implanted into the organic backbones, two types of AFMOFs were essentially afforded in our research group. In this review, we first pay some attention to 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 two 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:2018-07-14
  • Transition metal complexes as photosensitisers in one- and two-photon photodynamic therapy
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-04-19
    Luke K. McKenzie, Helen E. Bryant, Julia A. Weinstein

    Photodynamic therapy (PDT) exploits light-activated compounds for therapeutic use. It relies on a photosensitiser (PS) that is inactive in the absence of light. When irradiated, the PS absorbs light and is promoted to a higher energy, “excited” state (PS∗), which is either toxic to cells in itself or triggers formation of other species which are toxic to cells, and hence particular wavelengths of light can be used to induce light-dependent cell killing. In PDT occurring via the so-called type I and type II mechanisms, the PS∗ engages in energy transfer to dioxygen present in cells and tissues. This process generates highly reactive singlet oxygen (1O2) and/or other reactive oxygen species (ROS), which in turn cause damage in the immediate vicinity of the irradiation and ultimately can lead to cell death. Whilst the main focus of research for the last 50 years has been on organic molecules or porphyrins as sensitisers, there is now emerging interest in extending the use to transition metal (TM) complexes, which can display intense absorptions in the visible region, and many also possess high two-photon absorption cross-sections, enabling two-photon excitation with NIR light. As with any other type of photosensitiser, the issues to consider whilst designing a TM complex as a photosensitiser include cell permeability, efficient absorption of NIR light for deeper penetration, preferential affinity to cancer cells over healthy cells, targeted intracellular localisation and lack of side effects. This review summarises recent developments involving photosensitisers containing Ru(II), Os(II), Pt, Ir(III), and Re(I) ions, and the approaches used to address the above requirements. Several remarkable recent advances made in this area, including the first clinical trial of a metal complex as a photosensitiser, indicate the bright future of this class of compounds in PDT.

    更新日期:2018-07-14
  • Recent advances in copper complexes for electrical/light energy conversion
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-06-28
    Yurong Liu, Sze-Chun Yiu, Cheuk-Lam Ho, Wai-Yeung Wong

    A great deal of research effort has been put in green energy applications in the past few decades based on organic optoelectronics. Compared with conventional inorganic semiconductors, organic counterparts offer a much simpler strategy for low-cost mass production and structural modification. Hence, continuous and intensive academic and industrial research works have been done in these areas. In terms of the materials used, transition-metal complexes with the unique features of the transition metal centers represent a large group of candidates, showing high performance in energy conversion technologies. However, the commonly used transition metals, like Pt(II), Ir(III) and Ru(II), are expensive and of relatively low abundance. Concerning elemental sustainability and marketability, some abundant and cheaper metals should be investigated and further developed to replace these precious metals. Cu(I) complexes have shown their potentiality in solar energy harvesting and light emitting applications, due to their well-studied photophysics and structural diversity. In addition, copper is one of the earth-abundant metals with less toxicity, which makes it competitive to precious transition metals. As a result, a series of rational molecular engineering has been developed to boost the device performance of copper complexes. In this review, the recent progress of copper complexes in the fields of organic light emitting devices (OLEDs), photovoltaic cells (dye-sensitized solar cells (DSSCs) and bulk heterojunction solar cells (BHJSCs)) in the past two decades will be presented. Representative examples are chosen for discussion.

    更新日期:2018-06-30
  • 更新日期:2018-06-03
  • Stimuli responsive phthalocyanine-based fluorescent probes and photosensitizers
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2017-10-26
    Roy C.H. Wong, Pui-Chi Lo, Dennis K.P. Ng
    更新日期:2018-06-03
  • Photosensitization and controlled photosensitization with BODIPY dyes
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Heterogeneous catalysts based on mesoporous metal–organic frameworks
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Organelle-targeting metal complexes: From molecular design to bio-applications
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Weiss’ Reagents: A synthetically useful class of iodine(III) coordination compounds
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • 更新日期:2018-06-03
  • Recent advances in the assembly of high-nuclearity lanthanide clusters
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2017-11-11
    Xiu-Ying Zheng, Jing Xie, Xiang-Jian Kong, La-Sheng Long, Lan-Sun Zheng
    更新日期:2018-06-03
  • Recent progress in organohalide lead perovskites for photovoltaic and optoelectronic applications
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Homo and heterometallic gold(I) clusters with hypercoordinated carbon
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Europium-activated luminescent nanoprobes: From fundamentals to bioapplications
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Metallosalen-based crystalline porous materials: Synthesis and property
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2017-11-20
    Guozan Yuan, Hong Jiang, Liyan Zhang, Yan Liu, Yong Cui
    更新日期:2018-06-03
  • Chiral metal–organic cages/containers (MOCs): From structural and stereochemical design to applications
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Molecular magnetism of lanthanide: Advances and perspectives
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • 更新日期:2018-06-03
  • Molecular/polymeric metallaynes and related molecules: Solar cell materials and devices
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • 更新日期:2018-06-03
  • Bipyridinium derivative-based coordination polymers: From synthesis to materials applications
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2017-11-22
    Jian-Ke Sun, Xiao-Dong Yang, Guo-Yu Yang, Jie Zhang
    更新日期:2018-06-03
  • Transition metal-induced B–H functionalization of o-carborane
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Platinum coordination compounds with potent anticancer activity
    Coordin. Chem. Rev. (IF 14.499) 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. The purpose of this review is to provide some background in the history and development of platinum(II) and platinum(IV) complexes.

    更新日期:2018-06-03
  • Recent progress for reversible homogeneous catalytic hydrogen storage in formic acid and in methanol
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Luminescent single-molecule magnets based on lanthanides: Design strategies, recent advances and magneto-luminescent studies
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Metal–organic frameworks and porous organic polymers for sustainable fixation of carbon dioxide into cyclic carbonates
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Lanthanide complexes for luminescence-based sensing of low molecular weight analytes
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Harnessing the properties of cobalt coordination complexes for biological application
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Redox-coupled structural changes in copper chemistry: Implications for atom transfer catalysis
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Recent advances in post-synthetic modification of metal–organic frameworks: New types and tandem reactions
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Lanthanoid tetrazole coordination complexes
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Bright lights down under: Metal ion complexes turning the spotlight on metabolic processes at the cellular level
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Recent developments in the metallo-supramolecular chemistry of oligo-β-diketonato ligands
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2017-12-11
    Aidan J. Brock, 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:2018-06-03
  • Switchable cobalt coordination polymers: Spin crossover and valence tautomerism
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Catalytic properties of chemical transformation within the confined pockets of Werner-type capsules
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Reaction mechanisms of catalytic photochemical CO2 reduction using Re(I) and Ru(II) complexes
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • Kinetically-inert polypyridylruthenium(II) complexes as therapeutic agents
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2017-12-19
    Xin Li, Anil K. Gorle, Madhu K. Sundaraneedi, F. Richard Keene, J. Grant Collins
    更新日期:2018-06-03
  • Labelling proteins and peptides with phosphorescent d6 transition metal complexes
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2017-12-19
    Timothy U. Connell, Paul S. Donnelly
    更新日期:2018-06-03
  • 更新日期:2018-06-03
  • The photoluminescent metal nanoclusters with atomic precision
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • 更新日期:2018-06-03
  • Iridium complexes with monodentate N-heterocyclic carbene ligands
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2017-12-27
    Gellért Sipos, Reto Dorta
    更新日期:2018-06-03
  • Nickel complexes as molecular catalysts for water splitting and CO2 reduction
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2017-12-28
    Jia-Wei Wang, Wen-Ju Liu, Di-Chang Zhong, Tong-Bu Lu
    更新日期:2018-06-03
  • Proton conductive metal phosphonate frameworks
    Coordin. Chem. Rev. (IF 14.499) 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:2018-06-03
  • 更新日期:2018-06-03
  • Anion coordination chemistry: From recognition to supramolecular assembly
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-02-15
    Jie Zhao, Dong Yang, Xiao-Juan Yang, Biao Wu
    更新日期:2018-06-03
  • Anion receptor chemistry: Highlights from 2016
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-02-19
    Philip A. Gale, Ethan N.W. Howe, Xin Wu, Michael J. Spooner
    更新日期:2018-06-03
  • Recent advances in bidentate bis(N-heterocyclic carbene) transition metal complexes and their applications in metal-mediated reactions
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-02-23
    Michael G. Gardiner, Curtis C. Ho

    The advanced development of NHC chemistry has lead to an extensive array of NHC ligand classes varying in structural and electronic properties. Although monodentate NHC ligands are by far the most thoroughly studied, multi-dentate NHC ligands including bidentate, pincer, scorpionate and macrocyclic motifs along with their corresponding transition metal complexes are widely reported in the literature. The unique structural and electronic properties along with high degree of modularity inherent to NHC ligands has made them ideal candidates for the inclusion in chelate rings affording intriguing reactivity consequences in a wide range of transition metal-mediated reactions. This short review focuses on the recent developments of bidentate bis(NHC) transition metal complexes and their applications in contemporary metal-mediated reactions such as alkane oxidation, transfer hydrogenation and photochemical transformations.

    更新日期:2018-06-03
  • Metal–organic frameworks with catalytic centers: From synthesis to catalytic application
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-02-27
    Yan-Shang Kang, Yi Lu, Kai Chen, Yue Zhao, Peng Wang, Wei-Yin Sun
    更新日期:2018-06-03
  • Carboxylate covalently modified polyoxometalates: From synthesis, structural diversity to applications
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-02-27
    Pengtao Ma, Feng Hu, Jingping Wang, Jingyang Niu
    更新日期:2018-06-03
  • Computational studies of the nonlinear optical properties of organometallic complexes
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-03-08
    Mahesh S. Kodikara, Robert Stranger, Mark G. Humphrey

    Computational methods for calculating the molecular nonlinear optical (NLO) properties of molecules are reviewed, with an emphasis on clarifying the strengths and weaknesses of the various approaches. A brief introduction to the theory of NLO effects is provided, and a summary of the key experimental techniques for the determination of molecular first hyperpolarizabilities is included, with discussion of their advantages and disadvantages. Applications of semi-empirical methods and density functional theory in developing structure–quadratic NLO property relationships for organometallic complexes (and particularly metal alkynyl complexes) are reviewed.

    更新日期:2018-06-03
  • Magnetism in one-dimensional metal–nitronyl nitroxide radical system
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-03-09
    Xixi Meng, Wei Shi, Peng Cheng
    更新日期:2018-06-03
  • Biological applications of Ru(II) polypyridyl complexes
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-03-09
    Mariusz Mital, Zyta Ziora
    更新日期:2018-06-03
  • Luminescent oligonuclear metal complexes and the use in organic light-emitting diodes
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-03-13
    Qian-Chong Zhang, Hui Xiao, Xu Zhang, Liang-Jin Xu, Zhong-Ning Chen
    更新日期:2018-06-03
  • Molecular and supramolecular chemistry of mono- and di-selenium analogues of metal dithiocarbamates
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-03-15
    See Mun Lee, Peter J. Heard, Edward R.T. Tiekink
    更新日期:2018-06-03
  • Recent advances in ultraviolet and deep-ultraviolet second-order nonlinear optical crystals
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-03-15
    Chao Wu, Gang Yang, Mark G. Humphrey, Chi Zhang
    更新日期:2018-06-03
  • Recent advances about metal–organic frameworks in the removal of pollutants from wastewater
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-03-19
    Qiang Gao, Jian Xu, Xian-He Bu

    Water pollution is one of the most serious worldwide problems that endangers the survival and development of human society. Therefore, the effective and efficient removal of contaminants from water has become a hot topic. As a fast-growing branch of coordination chemistry, metal–organic frameworks (MOFs) with tailorable porous structures and numerous active sites have proved to be ideal adsorbents or photocatalysts for water purification. In this review, recent advances in the removal and degradation of water pollutants by MOFs are highlighted. In addition, the challenges and prospects in this active field are also briefly discussed.

    更新日期:2018-06-03
  • Tridentate pyridine–pyrrolide chelate ligands: An under-appreciated ligand set with an immensely promising coordination chemistry
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-03-28
    James N. McPherson, Biswanath Das, Stephen B. Colbran

    This review covers all aspects of the chemistry of metal complexes of tridentate κ3-N pyridine–pyrrolide ligands, from the syntheses of the ligands to what is known about the metal complexes – their structural and physical properties, and their reactivities, including use in catalytic processes. Applications of the complexes range from the switching elements in molecular devices, to luminophores in electroluminescent devices and photosensitisers in light-driven catalyses, to anticancer therapeutics and to efficient catalysts for organic transformations. The general properties of the ligands and metal complexes are deduced from the available literature, and areas of κ3-N pyridine–pyrrolide metal complex chemistry ripe for development are pinpointed.

    更新日期:2018-06-03
  • Optical limiting properties of (reduced) graphene oxide covalently functionalized by coordination complexes
    Coordin. Chem. Rev. (IF 14.499) Pub Date : 2018-05-16
    D.M. Aradhana S. Dissanayake, Marie P. Cifuentes, Mark G. Humphrey

    The nonlinear optical (NLO) and optical limiting (OL) properties of graphene oxide (GO), reduced graphene oxide (RGO), and particularly GO/RGO coordination complex hybrids are reviewed. A brief introduction to mechanisms of OL and a summary of the key measurement techniques for determining NLO/OL merit is provided. A summary of synthetic procedures to GO/RGO coordination complex hybrids is included.

    更新日期:2018-05-17
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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