Silver in the Center Enhances Room‐Temperature Phosphorescence of a Platinum Sub‐nanocluster by 18 Times

Akanuma, Yuki; Imaoka, Takane; Sato, Hiroyasu; Yamamoto, Kimihisa

doi:10.1002/anie.202012921

Cited by 30 publications

(17 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This "central lock-atom" strategy for the suppression of non-radiative transitions and the enhancement of PL is different from the previous strategy for the PL enhancement of gold nanoclusters which is based on surface engineering. [9,11,38,39] It should be noted that very recently, Yamamoto et al [40] reported that the central Ag atom could enhance the phosphorescence of platinum nanoclusters.…”

Section: Resultsmentioning

confidence: 99%

Bright NIR‐II Photoluminescence in Rod‐Shaped Icosahedral Gold Nanoclusters

Zeman

et al. 2021

Small

106

View full text Add to dashboard Cite

Fluorophores with high quantum yields, extended maximum emission wavelengths, and long photoluminescence (PL) lifetimes are still lacking for sensing and imaging applications in the second near‐infrared window (NIR‐II). In this work, a series of rod‐shaped icosahedral nanoclusters with bright NIR‐II PL, quantum yields up to ≈8%, and a peak emission wavelength of 1520 nm are reported. It is found that the bright NIR‐II emission arises from a previously ignored state with near‐zero oscillator strength in the ground‐state geometry and the central Au atom in the nanoclusters suppresses the non‐radiative transitions and enhances the overall PL efficiency. In addition, a framework is developed to analyze and relate the underlying transitions for the absorptions and the NIR‐II emissions in the Au nanoclusters based on the experimentally defined absorption coefficient. Overall, this work not only shows good performance of the rod‐shaped icosahedral series of Au nanoclusters as NIR‐II fluorophores, but also unravels the fundamental electronic transitions and atomic‐level structure‐property relations for the enhancement of the NIR‐II PL in gold nanoclusters. The framework developed here also provides a simple method to analyze the underlying electronic transitions in metal nanoclusters.

show abstract

Section: Resultsmentioning

confidence: 99%

Bright NIR‐II Photoluminescence in Rod‐Shaped Icosahedral Gold Nanoclusters

Zeman

et al. 2021

Small

106

View full text Add to dashboard Cite

show abstract

“…These considerations are even more dramatic when two different metal precursors are engaged, rendering the rational preparation of heterobimetallic entities extremely challenging. Postmodification strategies, such as doping of monometallic clusters with heterometal atoms, − or rearrangement of two independently synthesized monometallic clusters, − are emerging approaches that have attracted substantial interest recently, but so far are limited to thiolate or carbonyl metal clusters. Lability phenomena and metal exchange strategies in polyhydride metal clusters are much less investigated to date.…”

Section: Introductionmentioning

confidence: 99%

Rational Preparation of Well-Defined Multinuclear Iridium–Aluminum Polyhydride Clusters and Comparative Reactivity

et al. 2022

View full text Add to dashboard Cite

We report an original alkane elimination approach, entailing the protonolysis of triisobutylaluminium by the acidic hydrides from Cp*IrH4. This strategy allows access to a series of well-defined tri-and tetranuclear iridium aluminium polyhydride clusters, depending on the stoichiometry: 3) and [(Cp*IrH3)3Al] (4). Contrary to most transition metal aluminohydride complexes which can be considered as [AlHx+3] xaluminates and LnM + moieties, the situation here is reversed: these complexes have original structures which are best described as [Cp*IrHx] n-iridate units surrounding cationic Al(III) fragments. This is corroborated by reactivity studies, which show that the hydrides are always retained at the iridium sites and that the [Cp*IrH3] -moieties are labile and can be transmetallated to yield potassium ([KIrCp*H3], 8) or silver (([AgIrCp*H3]n, 10) derivatives of potential synthetic interest. DFT calculations show that the bonding situation can vary in these systems, from 3-centre 2-electron hydride-bridged Lewis adducts of the form Ir-H⇀Al, to direct polarized metal-metal interaction from donation of d-electrons of Ir to the Al metal, and both types of interactions are at place to some extent in each of these clusters.

show abstract

“…Metal cluster with atom precision is an important class of nanomaterial and has become an emerging field in recent years. − Because of their well-defined structures and unique physicochemical properties, metal clusters can be regarded as an ideal platform and provide an excellent opportunity to study the relationship between structure and property, thereby triggering widespread research enthusiasm from the academic community. − Doping with heteroatom(s) is an effective strategy to manipulate the structure and property of metal clusters. Compared with monometallic clusters, bimetallic clusters are more attractive for practical applications due to the significantly improved physicochemical properties induced by the synergistic effect. − Nowadays, great efforts have been made in doping gold clusters with group IB element (Ag or Cu), while less work has been conducted on doping with group IIB metals such as Cd. − The pioneer contribution of Cd-doped bimetallic clusters was demonstrated respectively by Wang et al and Yao et al in 2015. Using Au 25 (SR) 18 as a template for doping, they used one Cd atom to replace a Au atom at either the center or vertex of the icosahedral Au 13 core by slight regulating the reaction conditions. , From then on, more efforts have been devoted to fabricating Cd-doped metal clusters; importantly, the structure features and the intriguing properties of those clusters have been revealed. − For instance, Jin and co-workers reported the synthesis of [Au 19 Cd 2 (SR) 16 ] − cluster by tailoring the surface of [Au 23 (SR) 16 ] − via Cd doping, and the single-crystal X-ray analysis shows that the core of [Au 19 Cd 2 (SR) 16 ] − is identical to that of [Au 23 (SR) 16 ] − , while their surface structures are distinct .…”

Section: Introductionmentioning

confidence: 99%

Identifying the Real Chemistry of the Synthesis and Reversible Transformation of AuCd Bimetallic Clusters

et al. 2022

View full text Add to dashboard Cite

The capability of precisely constructing bimetallic clusters with atomic accuracy provides exciting opportunities for establishing their structure–property correlations. However, the chemistry (the charge state of precursors, the property of ligands, the amount of dopant, and so forth) dictating the fabrication of clusters with atomic-level control has been a long-standing challenge. Herein, based on the well-defined Au25(SR)18 cluster (SR = thiolates), we have systematically investigated the factors of steric hindrance and electronic effect of ligands, the charge state of Au25(SR)18, and the amount of dopant that may determine the structure of AuCd clusters. It is revealed that [Au19Cd3(SR)18]− can be obtained when a ligand of smaller steric hindrance is used, while Au24Cd(SR)18 is attained when a larger steric hindrance ligand is used. In addition, negatively charged [Au25(SR)18]− is apt to form [Au19Cd3(SR)18]− during Cd doping, while Au24Cd(SR)18 is produced when neutral Au25(SR)18 is used as a precursor. Intriguingly, the reversible transformation between [Au19Cd3(SR)18]− and Au24Cd(SR)18 is feasible by subtly manipulating ligands with different steric hindrances. Most importantly, by introducing the excess amount of dopant, a novel bimetallic cluster, Au4Cd4(SR)12 is successfully fabricated and its total structure is fully determined. The electronic structures and the chirality of Au4Cd4(SR)12 have been elucidated by density functional theory (DFT) calculations. Au4Cd4(SR)12 reported herein represents the smallest AuCd bimetallic cluster with chirality.

show abstract

Silver in the Center Enhances Room‐Temperature Phosphorescence of a Platinum Sub‐nanocluster by 18 Times

Cited by 30 publications

References 47 publications

Bright NIR‐II Photoluminescence in Rod‐Shaped Icosahedral Gold Nanoclusters

Bright NIR‐II Photoluminescence in Rod‐Shaped Icosahedral Gold Nanoclusters

Rational Preparation of Well-Defined Multinuclear Iridium–Aluminum Polyhydride Clusters and Comparative Reactivity

Identifying the Real Chemistry of the Synthesis and Reversible Transformation of AuCd Bimetallic Clusters

Contact Info

Product

Resources

About