High-Nuclearity Silver Clusters Templated by Carbonates Generated from Atmospheric Carbon Dioxide Fixation

Bian, Shudan; Wang, Quan‐Ming

doi:10.1021/ja8087696

Cited by 163 publications

(73 citation statements)

References 28 publications

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“…17 In the presence of tetramethylethylenediamine (TMEDA), the reaction of Bu t CCAg with AgOTf in methanol in air gave [Ag 17 (CCBu t ) 14 CO 3 ]OTf in good yield. Structural determination revealed that the cation [Ag 17 (CCBu t ) 14 CO 3 ] + consists of 17 silver atoms linked by 14 alkynyl ligands, and there is a templating carbonate ion enclosed in the middle (Figure 3).…”

Section: Silver Alkynyl Clusters With Anion Templatesmentioning

confidence: 99%

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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Section: Silver Alkynyl Clusters With Anion Templatesmentioning

confidence: 99%

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

2015

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“…19,20 Several polymetallic carbonate-containing systems have been described, showing not just interesting structural motifs but also bewildering physical properties. 20 Similarly, lanthanides are milestone entities in terms of their magnetism, and have also shown fascinating physical behaviours such as nuclear spin detection and manipulation 21,22 blocking of magnetisation at high temperatures 23–26 magnetic memory in chiral systems with a non-magnetic ground state 27 and, very recently, blocking magnetisation at the atomic level.…”

Section: Introductionmentioning

confidence: 99%

Exchange-bias quantum tunnelling in a CO₂-based Dy₄-single molecule magnet

et al. 2017

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“…[10] Although some CO 3 2À -bridged or -centered complexes have been disclosedand the CO 3 2À anion in them also originated from the fixation of atmospheric carbond ioxide, [11] nanosized clusters or cluster-based infinite architectures containing Cu II ions templatedby CO 3 2À from atmospheric CO 2 are rare. From the selfassemblyp oint of view,s uch ab ig cluster as ac luster building unit (CBU) or connecting node has rarely been found in the construction of coordination architectures.…”

Section: Introductionmentioning

confidence: 99%

Robust Cluster Building Unit: Icosanuclear Heteropolyoxocopperate Templated by Carbonate

Liu

Kozlevčar

Strauch

et al. 2015

Chemistry A European J

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The encapsulation of carbonate derived from atmospheric CO2 has resulted in an icosanuclear heteropolyoxocopperate, isolated as a metal-organic 1D chain, 2D sheet, or 3D framework, in which the Cu20 nanocluster represents the first eight-capped α-Keggin polyoxometalate with the late-transition-metal Cu(II) as the polyatom, CO3(2-) as the heteroanion, and OH(-) and suc(2-) or glu(2-) (H2suc=succinic acid; H2glu=glutaric acid) as the terminal ligands, which suggests a conceptual similarity to classical polyoxometalates. Even in the presence of competitive SO4(2-) in the assembly system, the CO3(2-) anion is still captured as a template to direct the formation of the Cu20 nanocluster, which indicates the stronger templation ability of CO3(2-) compared with SO4(2-). When other aliphatic dicarboxylates, such as glutaric acid, were used as ligands, the CO3(2-)-templated Cu20 nanocluster was maintained and acted as a cluster building unit (CBU) to be linked by two glutarate bridges to generate a distinct 1D metal-organic chain. This report presents not only a rare example of a huge anion-templated transition-metal cluster, but also its use as a robust CBU to construct novel coordination architectures. Variable-temperature magnetic susceptibility studies revealed that an antiferromagnetic interaction exists within the Cu20 nanocluster. The correlation between the coordination structure and the electron paramagnetic resonance spectra recorded of both powder and single-crystal samples are discussed in detail.

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High-Nuclearity Silver Clusters Templated by Carbonates Generated from Atmospheric Carbon Dioxide Fixation

Cited by 163 publications

References 28 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

Exchange-bias quantum tunnelling in a CO₂-based Dy₄-single molecule magnet

Robust Cluster Building Unit: Icosanuclear Heteropolyoxocopperate Templated by Carbonate

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High-Nuclearity Silver Clusters Templated by Carbonates Generated from Atmospheric Carbon Dioxide Fixation

Cited by 163 publications

References 28 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

Exchange-bias quantum tunnelling in a CO2-based Dy4-single molecule magnet

Robust Cluster Building Unit: Icosanuclear Heteropolyoxocopperate Templated by Carbonate

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Exchange-bias quantum tunnelling in a CO₂-based Dy₄-single molecule magnet