Thiacalix[4]arene: New protection for metal nanoclusters

Guan, Zong‐Jie; Zeng, Jiu-Lian; Nan, Zi‐Ang; Wan, Xian‐Kai; Lin, Yumei; Wang, Quan‐Ming

doi:10.1126/sciadv.1600323

Cited by 141 publications

(95 citation statements)

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“…[24][25][26][27] Based on the multiple coordination sites of -OH and -Sgroups on them, a series of large metal nanoclusters or nanocages, including Co 16 , Co 24 , Mn 24 , Co 32 , Ni 32 , and Ni 40 , have been reported by Liao and Hong groups. [28][29][30][31][32][33] However, thiacalix [4]arene-protected silver nanocluster is still rudimentary, and only two closely related p-tert-butylthiacalix [4]arene (H 4 TC4A)-capped reductive Ag 34 and Ag 35 nanoclusters have been reported. 34,35 Although the coordination sites of H 4 TC4A favor to support silver nanoclusters, the bulky skeleton of H 4 TC4A also brings a big challenge in growth of single crystals, which is very crucial to understand the structural details of both metal core and metal-ligand interface.…”

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A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

Wang

Gong

et al. 2020

Nat Commun

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Thiacalix [4]arenes as a family of promising ligands have been widely used to construct polynuclear metal clusters, but scarcely employed in silver nanoclusters. Herein, an aniontemplated Ag 88 nanocluster (SD/Ag88a) built from p-tert-butylthiacalix[4]arene (H 4 TC4A) is reported. Single-crystal X-ray diffraction reveals that C 4 -symmetric SD/Ag88a resembles a metal-organic super calix comprised of eight TC4A 4− as walls and 88 silver atoms as base, which can be deconstructed to eight [CrO 4 @Ag 11 (TC4A)(EtS) 4 (OAc)] secondary building units arranged in an annulus encircling a CrO 4 2− in the center. Local and global anion template effects from chromates are individually manifested in SD/Ag88a. The solution stability and hierarchical assembly mechanism of SD/Ag88a are studied by using electrospray mass spectrometry. The Ag 88 nanocluster represents the highest nuclearity metal cluster capped by TC4A 4− . This work not only exemplify the specific macrocyclic effects of TC4A 4− in the construction of silver nanocluster but also realize the shape heredity of TC4A 4− to overall silver super calix.

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A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

Wang

Gong

et al. 2020

Nat Commun

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“…the door to understanding the alkynyl-gold interface and discoveringm any potential members of this new family of clusters; [25] Zheng et al andW ang et al then prepared severala lkynyl-capped Au-Ag alloyed nanoclusters,i nw hich somei mportant phenomena wereo bserved such as the promoting effects of surface ligands on catalysis by metal nanoparticles, promotion effect of chloride on clusterformation and site preferences in alkynyl-protected multimetallic nanoclusters. [26][27][28][29] In addition, alkynyl-protected Au-Cu alloyedn anoclusters with an icosidodecahedral Cu 30 shell [30] and an alkynyl-Cu interface, and homoleptic alkynyl-protected gold nanoclusters Au 44 [31] and Au 36 [31] have also been reported recently.H owever,r eports of another potential system, alkynyl-stabilized Ag nanoclusters, remain scarce compared with the well-documented gold nanoclusters.S of ar,o nly several alkynyl-protected Ag nanoclusters, e.g.,A g 19 , [32] Ag 25 , [32] Ag 35 , [33] andA g 74 [34] have been structurally determined.…”

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An Atomically Precise Alkynyl‐Protected PtAg₄₂ Superatom Nanocluster and Its Structural Implications

Shen

Mizuta

2017

Chemistry An Asian Journal

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The synthesis and structure determination of an alkynyl-protected Pt-doped Ag superatom nanocluster, [PtAg (C≡CC H CH ) ](SbF ) (1), are reported. The metallic core of this cluster can be viewed as a concentric three-shell Russian doll comprising Pt@Ag @Ag , in which the missing icosidodecahedral Ag shell and a new structural unit, M , have been observed. On the surface of 1, 28 alkynyl groups and 4 SbF anions were found co-protecting it. The protective role of SbF in nanoclusters is unprecedented. Moreover, of the 28 alkynyl ligands, 12 are connected not only with the outermost Ag shell, but also the inner Ag shell through the twelve pentagonal faces of the outermost icosidodecahedral Ag shell. Overall, by determining the crystal structure of 1, we discovered the missing icosidodecahedral Ag shell and the protective effect of SbF anions and demonstrated a novel M structural unit and the unique penetrability of pentagonal faces.

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“…Due to the unique affinity to silver ions, the tendency of thiacalixarenes to form nanocages is especially promising as protection for silver nanoclusters. Nonfunctionalized p-tert-butylthiacalix [4]arene TCA-1 has been shown as an effective protecting agent for silver nanoclusters (containing 35 and 34 Ag atoms) [94].…”

Section: Synthesis and Application Of Thiacalix[4]arene-based Agnpsmentioning

confidence: 99%

The Role of Calix[n]arenes and Pillar[n]arenes in the Design of Silver Nanoparticles: Self-Assembly and Application

Padnya

Gorbachuk

Stoikov

2020

IJMS

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Silver nanoparticles (AgNPs) are an attractive alternative to plasmonic gold nanoparticles. The relative cheapness and redox stability determine the growing interest of researchers in obtaining selective plasmonic and electrochemical (bio)sensors based on silver nanoparticles. The controlled synthesis of metal nanoparticles of a defined morphology is a nontrivial task, important for such fields as biochemistry, catalysis, biosensors and microelectronics. Cyclophanes are well known for their great receptor properties and are of particular interest in the creation of metal nanoparticles due to a variety of cyclophane 3D structures and unique redox abilities. Silver ion-based supramolecular assemblies are attractive due to the possibility of reduction by “soft” reducing agents as well as being accessible precursors for silver nanoparticles of predefined morphology, which are promising for implementation in plasmonic sensors. For this purpose, the chemistry of cyclophanes offers a whole arsenal of approaches: exocyclic ion coordination, association, stabilization of the growth centers of metal nanoparticles, as well as in reduction of silver ions. Thus, this review presents the recent advances in the synthesis and stabilization of Ag (0) nanoparticles based on self-assembly of associates with Ag (I) ions with the participation of bulk platforms of cyclophanes (resorcin[4]arenes, (thia)calix[n]arenes, pillar[n]arenes).

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Thiacalix[4]arene: New protection for metal nanoclusters

Abstract: An organic macrocycle ligand is promising in precisely controlling the structures and optical properties of silver nanoclusters.

Cited by 141 publications

References 35 publications

A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

An Atomically Precise Alkynyl‐Protected PtAg₄₂ Superatom Nanocluster and Its Structural Implications

The Role of Calix[n]arenes and Pillar[n]arenes in the Design of Silver Nanoparticles: Self-Assembly and Application

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Thiacalix[4]arene: New protection for metal nanoclusters

Abstract: An organic macrocycle ligand is promising in precisely controlling the structures and optical properties of silver nanoclusters.

Cited by 141 publications

References 35 publications

A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

An Atomically Precise Alkynyl‐Protected PtAg42 Superatom Nanocluster and Its Structural Implications

The Role of Calix[n]arenes and Pillar[n]arenes in the Design of Silver Nanoparticles: Self-Assembly and Application

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An Atomically Precise Alkynyl‐Protected PtAg₄₂ Superatom Nanocluster and Its Structural Implications