Materials with circularly polarized luminescence (CPL) are especially fascinating due to the widespread potential applications in 3D displays, biological probes, security encoding, encrypted ...information transmission, and storage. Among these CPL‐active materials, the ones based on atomically precise coinage, namely, the metal coinage clusters, have attracted increasing attention due to their fascinating chiral structures and intriguing luminescence characteristics. Meanwhile, these clusters provide an ideal platform at the nanoscale for understanding the chiral transfer across the organic–inorganic interface. In this report, the recent progress in constructing enantiomerically pure chiral coinage metal clusters and the luminescent mechanism of coinage metal clusters in aggregated state are reviewed, respectively. Moreover, CPL‐active atomically precise coinage metal clusters and their design strategies are discussed in detail. Finally, challenges and opportunities for constructing atomically precise coinage metal clusters with excellent CPL properties are discussed.
The development of circularly polarized luminescence (CPL)‐active materials has attracted increasing attention due to their wide potential applications. In this work, the design strategies for chiral and luminescent coinage metal clusters are summarized. Then, the research progress in the CPL‐active atomically precise coinage metal clusters is reviewed. The potential directions and challenges for future research are discussed.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Atomically precise enantiomeric metal clusters are scarce, and copper(I) alkynyl clusters with intense circularly polarized luminescence (CPL) responses have not been reported. A pair of chiral ...alkynyl ligands, (R/S)‐2‐diphenyl‐2‐hydroxylmethylpyrrolidine‐1‐propyne (abbreviated as R/S‐DPM) we successfully prepared and single crystals were characterized of optically pure enantiomeric pair of atomically‐precise copper(I) clusters, Cu14(R/S‐DPM)8(PF6)6 (denoted as R/S‐Cu14), which feature bright red luminescence and CPL with a high luminescence anisotropy factor (glum). A dilute solution containing R/S‐Cu14 was nonluminescent and CPL inactive at room temperature. Crystallization‐ and aggregation‐induced emission (CIE and AIE, respectively) contribute to the triggering of the CPL of R/S‐Cu14 in the crystalline and aggregated states. Their AIE behavior and good biocompatibility indicated applications of these copper(I) clusters in cell imaging in HeLa and NG108‐15 cells.
Atomically precise chiral CuI alkynyl nanoclusters R/S‐Cu14 with inherent chirality were synthesized for the first time. Crystallization‐ and aggregation‐induced emission (CIE and AIE, respectively) trigger circularly polarized luminescence (CPL) with an unprecedented luminescence anisotropy factor (glum).
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
A visible-light-mediated radical allylation of primary amine-derived Katritzky salts with allylic sulfones via C(sp3)–N bond activation is reported, furnishing the corresponding alkenes in ...satisfactory yields. This mild protocol provides an efficient strategy for site-specific C(sp3)–C(sp3) bond formation using abundant feedstock primary amines, particularly α-amino acids as alkyl radical precursors. This photocatalytic reaction demonstrates a broad substrate scope and good functional group tolerance.
An efficient and mild method was developed for the synthesis of 6-alkylated phenanthridines upon visible light irradiation. Bench-stable and easily handled redox-active Katritzky pyridinium salts ...derived from abundant amino acids/peptides were used as radical precursors for the alkylation of isocyanobiphenyl species. The reaction displays an excellent functional group tolerance and a potential utility for peptide functionalization, allowing access to desired products in good to excellent yields.
We report a new enantiomeric pair of superatomic silver clusters, R/S-Ag 17 , prepared from chiral alkynyl ligands. R-Ag 17 and S-Ag 17 possess C 3 symmetry and emit near-infrared (NIR) light with a ...quantum yield (QY) of 8.0% under ambient condition as well as NIR circularly polarized luminescence (CPL) as a result of the chirality of the excited states. Both experiments and theoretical calculations indicate for the first time that the CPL originates from transitions between superatomic 1P z (along the C 3 axis) and 1S orbitals. This work opens a new avenue for CPL-active metal nanoclusters by utilizing chiral alkynyl ligands and enlightens the chirality transfer from chiral protecting ligands to superatomic states in metal clusters.
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IJS, KILJ, NUK, PNG, UL, UM
Firm location affects firm risk through local factor prices. We find more procyclical factor prices such as wages and real estate prices in areas with more cyclical economies, namely, high "local ...beta" areas. While procyclical wages provide a natural hedge against aggregate shocks and reduce firm risk, procyclical prices of real estate, which are part of firm assets, increase firm risk. We confirm that firms located in higher local beta areas have lower industry-adjusted returns and conditional betas, and show that the effect is stronger among firms with low real estate holdings. A production-based equilibrium model explains these empirical findings.
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BFBNIB, FZAB, GIS, IJS, INZLJ, KILJ, NLZOH, NMLJ, NUK, OILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK, ZRSKP
Lithium‐ion hybrid supercapacitors (LIHSs), also called Li‐ion capacitors, have attracted much attention due to the combination of the rapid charge–discharge and long cycle life of supercapacitors ...and the high energy‐storage capacity of lithium‐ion batteries. Thus, LIHSs are expected to become the ultimate power source for hybrid and all‐electric vehicles in the near future. As an electrode material, graphene has many advantages, including high surface area and porous structure, high electric conductivity, and high chemical and thermal stability, etc. Compared with other electrode materials, such as activated carbon, graphite, and metal oxides, graphene‐based materials with 3D open frameworks show higher effective specific surface area, better control of channels, and higher conductivity, which make them better candidates for LIHS applications. Here, the latest advances in electrode materials for LIHSs are briefly summarized, with an emphasis on graphene‐based electrode materials (including 3D graphene networks) for LIHS applications. An outlook is also presented to highlight some future directions.
Lithium‐ion hybrid supercapacitors (LIHSs) attract much attention due to the combination of the rapid charge–discharge and long cycle life of supercapacitors and the high energy‐storage capacity of lithium‐ion batteries. The latest advances in electrode materials based on graphene (including 3D graphene) for LIHSs applications are summarized, and an outlook to highlight some future directions is presented.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
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•The development of alkynyl ligands for the preparation of coinage metal clusters was reviewed.•A comprehensive survey of synthetic methods of alkynyl-protected coinage metal clusters ...was presented.•The functional alkynyl-protected coinage metal clusters were classified and discussed.•The future development trends of alkynyl-protected coinage metal clusters were prospected.
The selection of surface organic ligands is very important for the preparation of coinage metal clusters with precise structures, which can dictate the related properties of metal clusters. Alkynyl ligands, as a class of protecting ligands in metal cluster systems, have been gaining attentions because of the characteristics of both π and σ coordination modes. Specially, alkynyl-protected coinage metal clusters possess rich properties. However, there is no review to systemically summarize the functional properties and structure-functionality correlations of alkynyl-protected coinage metal clusters. In this review, the development of alkynyl ligands for the preparation of coinage metal clusters was reviewed. Additionally, the synthetic approaches of the alkynyl-protected coinage metal clusters were provided. Then, the functional properties of the alkynyl-protected coinage metal clusters were comprehensively summarized. In the end, the prospects and opportunities for the future development were discussed. We believed that the review will motivate the development of functionality-oriented alkynyl-protected coinage metal clusters.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
As a type of energy storage device between traditional capacitors and batteries, the supercapacitor has the advantages of energy saving and environmental protection, high power density, fast charging ...and discharging speed, long cycle life, and so forth. One of the key factors affecting the performance of supercapacitor is the electrode material. Carbon materials, such as carbon nanotube, graphene, activated carbon, and carbon nanocage, are most widely concerned in the application of supercapacitors. The synergistic effect of composites can often obtain excellent results, which is one of the common strategies to increase the electrochemical performance of supercapacitors. To further improve the performance of binary composites, it is a relatively simple method to increase the components as the “bridge” between the two materials to form the ternary composites. The review mainly introduces the current research progress of supercapacitors with pure carbon nanomaterials and multistage carbon nanostructures (composites) as electrodes. The characteristics and application directions of different pure carbon nanomaterials are introduced in detail. Different ways of multilevel structure (material) composite have their own effects on the development of high‐performance supercapacitors. We also highlight the recent advances related to these fields and provide our insight into high‐energy supercapacitors.
Strategies and structures of supercapacitors prepared with diverse carbonaceous materials and various methods.The review mainly introduces the current research progress of supercapacitors with carbon nanostructures (composites) as electrodes. Different ways of multi‐level structure have their own effects on the development of high performance supercapacitors. We also highlight the recent advances related to these fields and provide our insight into high‐energy supercapacitors.
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The characteristics and application directions of different pure carbon nanomaterials and the structure construction of multilevel structures (composites) are introduced.
It is analyzed that different multilayer structures (materials) have different effects on the development of high‐performance supercapacitors.
The application and development direction of carbon nanomaterials in supercapacitors are prospected, which provides some guidance for the research of carbon nanomaterials for supercapacitors.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
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