A Facile Template Approach to High‐Nuclearity Silver(I) Alkynyl Clusters

Bian, Shudan; Wu, Hua-Bin; Wang, Quan‐Ming

doi:10.1002/anie.200902279

Cited by 157 publications

(46 citation statements)

References 19 publications

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“…18 Tetrahedral anions such as chromate and sulfate were chosen as the directing agents to demonstrate this synthetic method. Cluster 21 ).…”

Section: Silver Alkynyl Clusters With Anion Templatesmentioning

confidence: 99%

“…CCBu t )18 CrO 4 ](BF 4 ) 2 was prepared through the reaction of [Bu t CCAg] n with AgBF 4 followed by addingK 2 Cr 2 O 7 in the presence of TMEDA. Under the reaction condition (pH ∼ 8)The incorporation of chromates into the silver system could be easily verified as a yellow solution formed (characteristic of CrO 4 2− ) and yellow crystals of [Ag 22 (C CBu t ) 18 CrO 4 ](BF 4 ) 2 were isolated.…”

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Role of Anions Associated with the Formation and Properties of Silver Clusters

2015

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Metal clusters have been very attractive due to their aesthetic structures and fascinating properties. Different from nanoparticles, each cluster of a macroscopic sample has a well-defined structure with identical composition, size, and shape. As the disadvantages of polydispersity are ruled out, informative structure-property relationships of metal clusters can be established. The formation of a high-nuclearity metal cluster involves the organization of metal ions into a complex entity in an ordered way. To achieve controllable preparation of metal clusters, it is helpful to introduce a directing agent in the formation process of a cluster. To this end, anion templates have been used to direct the formation of high nuclearity clusters. In this Account, the role of anions played in the formation of a variety of silver clusters has been reviewed. Silver ions are positively charged, so anionic species could be utilized to control the formation of silver clusters on the basis of electrostatic interactions, and the size and shape of the resulted clusters can be dictated by the templating anions. In addition, since the anion is an integral component in the silver clusters described, the physical properties of the clusters can be modulated by functional anions. The templating effects of simple inorganic anions and polyoxometales are shown in silver alkynyl clusters and silver thiolate clusters. Intercluster compounds are also described regarding the importance of anions in determining the packing of the ion pairs and making contribution to electron communications between the positive and negative counterparts. The role of the anions is threefold: (a) an anion is advantageous in stabilizing a cluster via balancing local positive charges of the metal cations; (b) an anion template could help control the size and shape of a cluster product; (c) an anion can be a key factor in influencing the function of a cluster through bringing in its intrinsic properties. Properties including electron communication, luminescent thermochromism, single-molecule magnet, and intercluster charge transfer associated with anion-directed silver clusters have been discussed. We intend to attract chemists' attention to the role that anions could play in determining the structures and properties of metal complexes, especially clusters. We hope that this Account will stimulate more efforts in exploiting new role of anions in various metal cluster systems. Anions can do much more than counterions for charge balance, and they should be considered in the design and synthesis of cluster-based functional materials.

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“…18 Tetrahedral anions such as chromate and sulfate were chosen as the directing agents to demonstrate this synthetic method. Cluster 21 ).…”

Section: Silver Alkynyl Clusters With Anion Templatesmentioning

confidence: 99%

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confidence: 99%

Role of Anions Associated with the Formation and Properties of Silver Clusters

2015

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“…Anion-template is an effective approach to successfully attain polynuclear silver clusters with core-shell architectures. [14][15][16][17] In addition, simple silver thiol clusters withouta nion-template can be further fabricated by other multi-functionalized thiol ligands or other bridging ligandst ob uild new silver clusters. [10, 17] It is provedt ob eagood methodt oo btain stable silver cluster compounds with wonderful structures and remarkable functionalities.…”

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A Temperature‐Sensitive Luminescent Ag₄₂ Nanocluster Supported by TertButyl Thiol Ligands

Feng

Gao

Shi

et al. 2019

Chemistry An Asian Journal

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Compound [Ag42S5(StBu)25(CF3COO)4(CO3)](CO3)0.5⋅CH2Cl2⋅4CH3OH⋅9DMF (1) has been obtained and well defined. It consists of a multi‐shell structure involving two Ag centres, one Ag5S5 pentagram, two Ag5S5 pentagons and one Ag25S15 shell. Compound 1 has been characterized by XPS, FT‐IR, PXRD, TGA, NMR, MS, UV/Vis spectrum, TEM and cyclic voltammetry. Temperature‐sensitive luminescent property of 1 has also been investigated.

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“…[24][25][26][27] As the key intermediates in alkyne activation, silver acetylides are very mild and have very low basicity, and thus are very useful in the synthesis of complex molecules. In contrast, silver acetylides, especially silver phenylacetylide (SPA), are fundamental building blocks for the construction of diverse silver chains, high-nuclearity silver clusters and cages, [25,[35][36][37][38][39] and have been used to prepare silver nanowires. In contrast, silver acetylides, especially silver phenylacetylide (SPA), are fundamental building blocks for the construction of diverse silver chains, high-nuclearity silver clusters and cages, [25,[35][36][37][38][39] and have been used to prepare silver nanowires.…”

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“…[28][29][30][31][32][33][34] However, because of their low solubility and explosive and reactive nature, the structural information on these intermediates is rare, but critical to better understand their catalysis. In contrast, silver acetylides, especially silver phenylacetylide (SPA), are fundamental building blocks for the construction of diverse silver chains, high-nuclearity silver clusters and cages, [25,[35][36][37][38][39] and have been used to prepare silver nanowires. [40] Considerable efforts have been made to elucidate the structural aspects of SPA.…”

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A Robust Microfluidic Device for the Synthesis and Crystal Growth of Organometallic Polymers with Highly Organized Structures

Liu

Han

et al. 2014

Angew Chem Int Ed

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A simple and robust microfluidic device was developed to synthesize organometallic polymers with highly organized structures. The device is compatible with organic solvents. Reactants are loaded into pairs of reservoirs connected by a 15 cm long microchannel prefilled with solvents, thus allowing long-term counter diffusion for self-assembly of organometallic polymers. The process can be monitored, and the resulting crystalline polymers are harvested without damage. The device was used to synthesize three insoluble silver acetylides as single crystals of X-ray diffraction quality. Importantly, for the first time, the single-crystal structure of silver phenylacetylide was determined. The reported approach may have wide applications, such as crystallization of membrane proteins, synthesis and crystal growth of organic, inorganic, and polymeric coordination compounds, whose single crystals cannot be obtained using traditional methods.

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A Facile Template Approach to High‐Nuclearity Silver(I) Alkynyl Clusters

Cited by 157 publications

References 19 publications

Role of Anions Associated with the Formation and Properties of Silver Clusters

Role of Anions Associated with the Formation and Properties of Silver Clusters

A Temperature‐Sensitive Luminescent Ag₄₂ Nanocluster Supported by TertButyl Thiol Ligands

A Robust Microfluidic Device for the Synthesis and Crystal Growth of Organometallic Polymers with Highly Organized Structures

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A Facile Template Approach to High‐Nuclearity Silver(I) Alkynyl Clusters

Cited by 157 publications

References 19 publications

Role of Anions Associated with the Formation and Properties of Silver Clusters

Role of Anions Associated with the Formation and Properties of Silver Clusters

A Temperature‐Sensitive Luminescent Ag42 Nanocluster Supported by TertButyl Thiol Ligands

A Robust Microfluidic Device for the Synthesis and Crystal Growth of Organometallic Polymers with Highly Organized Structures

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A Temperature‐Sensitive Luminescent Ag₄₂ Nanocluster Supported by TertButyl Thiol Ligands