Observation of a new type of aggregation-induced emission in nanoclusters

Kang, Xi; Wang, Shuxin; Zhu, Manzhou

doi:10.1039/c7sc05317g

Cited by 128 publications

(126 citation statements)

References 61 publications

(44 reference statements)

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“…Specifically, a 6.6‐fold enhancement has been observed in the temperature reducing process . Such an enhancement was induced by the reduced energy consumption of thermal vibrations of nanoclusters, which has also been observed in the PL of Pt 1 Ag 28 and Ag 29 nanoclusters …”

Section: Properties Of Ser‐stabilized Nanoclustersmentioning

confidence: 80%

Metal Nanoclusters Stabilized by Selenol Ligands

Kang

Zhu

2019

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The past decades have witnessed great advances in controllable synthesis, structure determination, and property investigation of metal nanoclusters. Selenolated nanoclusters, a special branch in the nanocluster family, have attracted great interest in these years. The electronegativity and atomic radius of selenium is different from sulfur, and thus the selenolated nanoclusters are anticipated to display different electronic/geometric structures and distinct chemical/physical properties relative to their thiolated analogues. This review covers the syntheses, structures, and properties of selenolated nanoclusters (including Au, Ag, Cu, and alloy nanoclusters). Ligand effects (between SeR and SR) on nanocluster properties, including optical absorption, stability, and electrochemical properties, are disclosed as well. At the end of the review, a scope for improvements and future perspectives of selenolated nanoclusters is highlighted. The review hopefully opens up new horizons for cluster scientists to synthesize more selenolated nanoclusters with novel structures and properties. This review is based on publications available up to May 2019.

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Section: Properties Of Ser‐stabilized Nanoclustersmentioning

confidence: 80%

Metal Nanoclusters Stabilized by Selenol Ligands

Kang

Zhu

2019

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“…1E and fig. S3) and subsequently discussed temperature-dependent luminescence further corroborate the high thermostability of these enantiomeric silver clusters in air, which is a rare property in ligand-protected silver clusters, including mixed-valence and normal-valence ones (11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25).…”

Section: Synthesis and Characterizationmentioning

confidence: 54%

“…However, because of the well-known inherent susceptibility of silver, the number of stable atomically precise silver clusters in oxidized or reduced states under ambient conditions or at higher temperatures remains very limited (11)(12)(13), and all of them suffer from low quantum efficiency or nonluminescence (16)(17)(18)(19)(20)(21)(22)(23)(24)(25). The reported quantum yield (QY) record is 6.6% for atomically precise Ag(I) clusters from ligand-based emission (24) and 11.7% for mixed-valence ones from aggregation-induced emission in solution (25), preventing understanding of the fundamental cluster structure-photoluminescence relations and restricting the development of their applications as lighting materials. Hence, the designed construction of atomically precise monolayer-protected silver clusters having a satisfactory photoluminescence QY (PLQY) and stability at high temperature in air for future practical application remains a practical challenge, probably because the usual ligand-to-metal charge transfer (LMCT) transition responsible for the PL of silver clusters has intrinsic lower emission efficiency (3,(16)(17)(18)(19)(20)(21)(22)(23)(24)(25).…”

Section: Introductionmentioning

confidence: 99%

Ultrastable atomically precise chiral silver clusters with more than 95% quantum efficiency

et al. 2020

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Monolayer-protected atomically precise silver clusters display low photoluminescence (PL) quantum yield (QY) and susceptibility under ambient conditions, and their chiroptical activities also remain underdeveloped. Here, we report enantiomers of an octahedral Ag6 cluster prepared via one-step synthesis using designed chiral ligands at ambient temperature. These clusters exhibit a highest PLQY (300 K) >95.0% and retain their structural integrity and emission up to 150°C in air. Atomically precise structural determination combined with photophysical and computational analysis revealed that thermally activated delayed fluorescence, observed in silver cluster systems, is responsible for the high PLQY, which combines chirality in excited states to generate strong circularly polarized luminescence. These unprecedented findings open up horizons of investigation of monolayer-protected silver clusters for future luminescence applications.

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“…2B and S1 ‡), demonstrating the dissociation-aggregation pattern of PPh 3 ligands on the Ag 29 nanocluster surface. 63 However, the [Na 1 (NMP) 5 ] + and [Na 3 (DMF) 12 ] 3+ were undetectable in the ESI-MS, which was proposed to result from the weak interactions between Na + cations and NMP/DMP molecules causing such solventconjoined cations to decompose in mass spectroscopy. 23 Na NMR was performed to verify the presence of Na + or Na +conjoined cations in these nanoclusters.…”

Section: Resultsmentioning

confidence: 99%

Rendering hydrophobic nanoclusters water-soluble and biocompatible

et al. 2020

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Hydrophobic and hydrophilic nanoclusters embody complementary superiorities. The means to amalgamate these superiorities, i.e., the atomic precision of hydrophobic clusters and the water dissolvability of hydrophilic clusters, remains challenging. This work presents a versatile strategy to render hydrophobic nanoclusters water-soluble-the micellization of nanoclusters in the presence of solvent-conjoined Na + cations-which overcomes the above major challenge. Specifically, although [Ag 29 (SSR) 12 (PPh 3 ) 4 ] 3À nanoclusters are absolutely hydrophobic, they show good dissolvability in aqueous solution in the presence of solvent-conjoined Na + cations (Na 1 (NMP) 5 or Na 3 (DMF) 12 ). Such cations act as both counterions of these nanoclusters and surface cosolvent of cluster-based micelles in the aqueous phase. A combination of DLS (dynamic light scattering) and aberration-corrected HAADF-STEM (high angle annular dark field detector scanning transmission electron microscopy) measurements unambiguously shows that the phase-transfer of hydrophobic Ag 29 into water is triggered by the micellization of nanoclusters. Owing to the excellent water solubility and stability of [Ag 29 (SSR) 12 (PPh 3 ) 4 ] 3À [Na 1 (NMP) 5 ] 3 + in H 2 O, its performance in cell staining has been evaluated.Furthermore, the general applicability of the micellization strategy has been verified. Overall, this work presents a convenient and efficient approach for the preparation of cluster-based, biocompatible nanomaterials.

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Observation of a new type of aggregation-induced emission in nanoclusters

Abstract: A novel mechanism of aggregation-induced emission defined as the restriction of the ligand dissociation–aggregation process in the nanocluster range is proposed.

Cited by 128 publications

References 61 publications

Metal Nanoclusters Stabilized by Selenol Ligands

Metal Nanoclusters Stabilized by Selenol Ligands

Ultrastable atomically precise chiral silver clusters with more than 95% quantum efficiency

Rendering hydrophobic nanoclusters water-soluble and biocompatible

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