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A 'passivated precursor' approach is developed for the efficient synthesis and isolation of all‐alkynyl‐protected gold nanoclusters. Direct reduction of dpa‐passivated precursor Au‐dpa (Hdpa=2,2'‐dipyridylamine) in one‐pot under ambient conditions gives a series of clusters including Au22(C≡CR)18 (R=−C6H4−2−F), Au36(C≡CR)24, Au44(C≡CR)28, Au130(C≡CR)50, and Au144(C≡CR)60. These clusters can be well separated via column chromatography. The overall isolation yield of this series of clusters is 40 % (based on gold), which is much improved in comparison with previous approaches. It is notable that the molecular structure of the giant cluster Au130(C≡CR)50 is revealed, which presents important information for understanding the structure of the mysterious Au130 nanoclusters. Theoretical calculations indicated Au130(C≡CR)50 has a smaller HOMO‐LUMO gap than Au130(S−C6H4−4−CH3)50. This facile and reliable synthetic approach will greatly accelerate further studies on all‐alkynyl‐protected gold nanoclusters. [ABSTRACT FROM AUTHOR]

The application of supramolecular templates in aligning atomically precise heterometal arrays is important for pursuing functional materials. Herein, we report that a bilayered supramolecular tri‐deprotonated melamine dimer functions as an effective template in the construction of a heterometallic gold(I)‐silver(I) macrocyclic cluster [μ6‐(C3N6H3)3−]2−AuI6AgI6. X‐ray single crystal structural analysis showed that a crown‐like AuI6AgI6 macrocycle is aligned around two parallelly stacked μ6‐(C3N6H3)3− moieties hold together with π–π interactions. Theoretical calculations revealed that the [μ6‐(C3N6H3)3−]2 motif dominantly contributes to the near‐occupied orbitals in the electronic structure, which is closely related to its luminescence properties. This work demonstrates that the supramolecular templates containing multiple symmetric binding sites may present a facile approach in the construction of functional metal clusters. [ABSTRACT FROM AUTHOR]

A 'passivated precursor' approach is developed for the efficient synthesis and isolation of all‐alkynyl‐protected gold nanoclusters. Direct reduction of dpa‐passivated precursor Au‐dpa (Hdpa=2,2'‐dipyridylamine) in one‐pot under ambient conditions gives a series of clusters including Au22(C≡CR)18 (R=−C6H4−2−F), Au36(C≡CR)24, Au44(C≡CR)28, Au130(C≡CR)50, and Au144(C≡CR)60. These clusters can be well separated via column chromatography. The overall isolation yield of this series of clusters is 40 % (based on gold), which is much improved in comparison with previous approaches. It is notable that the molecular structure of the giant cluster Au130(C≡CR)50 is revealed, which presents important information for understanding the structure of the mysterious Au130 nanoclusters. Theoretical calculations indicated Au130(C≡CR)50 has a smaller HOMO‐LUMO gap than Au130(S−C6H4−4−CH3)50. This facile and reliable synthetic approach will greatly accelerate further studies on all‐alkynyl‐protected gold nanoclusters. [ABSTRACT FROM AUTHOR]

Due to the stability issue, It is difficult to prepare a silver nanocluster bearing functional sites, especially at a large scale. We report the synthesis and structure of a stable silver nanocluster bearing multiple surface aldehyde groups [Ag21(Ph2PO2)10(p‐CHOPhC≡C)6]SbF6, which allows for postsynthesis modification such as surface functionalization through aldimine condensation to give homochiral clusters. Remarkably, the preparation of this cluster can be done in ~90 % high yield at gram scale, which facilitates further studies and potential applications. Through DFT calculations and geometric structure analysis, the high stability of this cluster is attributed to the geometric closure and electronic structure. This is the first time that an effective one‐pot method has been developed to synthesize functional silver nanoclusters in high yield. The title cluster will be useful in the development of a variety of cluster‐based materials. [ABSTRACT FROM AUTHOR]

It is challenging to attain strong near-infrared (NIR) emissive gold nanoclusters. Here we show a rod-shaped cluster with the composition of [Au 28 (p-MBT) 14 (Hdppa) 3 ](SO 3 CF 3 ) 2 (1 for short, Hdppa is N,N-bis(diphenylphosphino)amine, p-MBT is 4-methylbenzenethiolate) has been synthesized. Single crystal X-ray structural analysis reveals that it has a rod-like face-centered cubic (fcc) Au 22 kernel built from two interpenetrating bicapped cuboctahedral Au 15 units. 1 features NIR luminescence with an emission maximum at 920 nm, and the photoluminescence quantum yield (PLQY) is 12%, which is 30-fold of [Au 21 (m-MBT) 12 (Hdppa) 2 ]SO 3 CF 3 (2, m-MBT is 3-methylbenzenethiolate) with a similar composition and 60-fold of Au 30 S(S‑t‑Bu) 18 with a similar structure. time-dependent DFT(TDDFT)calculations reveal that the luminescence of 1 is associated with the Au 22 kernel. The small Stokes shift of 1 indicates that it has a very small excited state structural distortion, leading to high radiative decay rate (k r ) probability. The emission of cluster 1 is a mixture of phosphorescence and thermally activated delayed fluorescence(TADF), and the enhancement of the NIR emission is mainly due to the promotion of k r rather than the inhibition of k nr . This work demonstrates that the metal kernel and the surface structure are both very important for cluster-based NIR luminescence materials., (© 2024. The Author(s).)

A 'passivated precursor' approach is developed for the efficient synthesis and isolation of all-alkynyl-protected gold nanoclusters. Direct reduction of dpa-passivated precursor Au-dpa (Hdpa=2,2'-dipyridylamine) in one-pot under ambient conditions gives a series of clusters including Au 22 (C≡CR) 18 (R=-C 6 H 4 -2-F), Au 36 (C≡CR) 24 , Au 44 (C≡CR) 28 , Au 130 (C≡CR) 50 , and Au 144 (C≡CR) 60 . These clusters can be well separated via column chromatography. The overall isolation yield of this series of clusters is 40 % (based on gold), which is much improved in comparison with previous approaches. It is notable that the molecular structure of the giant cluster Au 130 (C≡CR) 50 is revealed, which presents important information for understanding the structure of the mysterious Au 130 nanoclusters. Theoretical calculations indicated Au 130 (C≡CR) 50 has a smaller HOMO-LUMO gap than Au 130 (S-C 6 H 4 -4-CH 3 ) 50 . This facile and reliable synthetic approach will greatly accelerate further studies on all-alkynyl-protected gold nanoclusters., (© 2024 Wiley-VCH GmbH.)

The application of supramolecular templates in aligning atomically precise heterometal arrays is important for pursuing functional materials. Herein, we report that a bilayered supramolecular tri-deprotonated melamine dimer functions as an effective template in the construction of a heterometallic gold(I)-silver(I) macrocyclic cluster [μ 6 -(C 3 N 6 H 3 ) 3- ] 2 -Au I 6 Ag I 6 . X-ray single crystal structural analysis showed that a crown-like Au I 6 Ag I 6 macrocycle is aligned around two parallelly stacked μ 6 -(C 3 N 6 H 3 ) 3- moieties hold together with π-π interactions. Theoretical calculations revealed that the [μ 6 -(C 3 N 6 H 3 ) 3- ] 2 motif dominantly contributes to the near-occupied orbitals in the electronic structure, which is closely related to its luminescence properties. This work demonstrates that the supramolecular templates containing multiple symmetric binding sites may present a facile approach in the construction of functional metal clusters., (© 2023 Wiley-VCH GmbH.)