Anion-Templated Syntheses of Rhombohedral Silver-Alkynyl Cage Compounds

Rais, Daniela; Yau, J.K.F.; Mingos, D. Michael P.; Vilar, Ramón; White, Andrew J. P.; Williams, David J.

doi:10.1002/1521-3773(20010917)40:18<3464::aid-anie3464>3.0.co;2-m

Cited by 248 publications

(126 citation statements)

References 74 publications

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“…12 Cl]OH. 14,15 This silver(I) cluster consists of 14 silver(I) ions and 12 tertbutylacetylide ligands and an enclosed chloride ion. The silver(I) centers are in an arrangement of a near-regular rhombic dodecahedron of O h symmetry ( Figure 1).…”

Section: Silver Alkynyl Clusters With Anion Templatesmentioning

confidence: 99%

“…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). The Ag−O bond distances are between 2.39 and 2.84 Å.…”

Section: Silver Alkynyl Clusters With Anion Templatesmentioning

confidence: 99%

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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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Section: Silver Alkynyl Clusters With Anion Templatesmentioning

confidence: 99%

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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“…An (+)-ESI high-resolution mass spectrum clearly showed the molecular ion peak at m/z = 355.1052, corresponding to C 14 as 56 -62 S mol −1 cm 2 , which is much lower than the value of 120 -160 S mol −1 cm 2 expected for 1 : 1 electrolytes [23]. This points to a balanced solution equilibrium between salt 2A and one or more ion-paired species; one such species could be 2B, which features an Ag(I)-Ag(I) interaction.…”

Section: Resultsmentioning

confidence: 99%

Molecular and Crystal Structure of Chlorido[2-(N,N,N',N'- tetramethylamidinio)ethynido]silver

Weingärtner

Maas

2013

Zeitschrift Für Naturforschung B

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The solid-state structure of chlorido [2-(N,N,N ,N -tetramethylamidinio)ethynido]silver (3), obtained by C(sp)-metalation of N,N,N ,N -tetramethyl-propiolamidinium chloride with silver(I) oxide, has been determined by X-ray diffraction analysis. A comparison of bond lengths in the propiolamidinium moiety with those of the two genuine propiolamidinium salts 4 and 5, as well as with data for the isolated N,N,N ,N -tetramethyl-propiolamidinium cation obtained by quantum-chemical calculations, has been made. It can be concluded that complex 3 is better described as a (tetramethylamidinio)ethynyl than as a 3,3-bis(dimethylamino)allenylidene silver complex.

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“…The other F2 of HF 2 − also encapsulated in the pseudo cavity and H-bonded with amide hydrogen H7A and two aromatic hydrogens H11 and H46. the NO 3 − ion by analyzing the crystal structure of the complex [L 2 H·NO 3 ·H 2 O] (8). 41 Moreover, a close inspection of the H-bond interaction between carbonyl and CH resulted in a dimeric like structure of the receptor where O4 acts as an acceptor from H34A and H36.…”

Section: Crystal Structure Studiesmentioning

confidence: 99%

Anion complexation with cyanobenzoyl substituted first and second generation tripodal amide receptors: crystal structure and solution studies

2015

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Anion complexation properties of two new tripodal amide receptors have been extensively studied here. Two tripodal receptors have been synthesized from the reaction of cyanobenzoyl acid chloride with two tri-amine building blocks such as (i) tris(2-aminoethyl)amine and (ii) tris(2-(4-aminophenoxy)ethyl)amine, which resulted in the first (L1) and second (L2) generation tripodal amides respectively. A detailed comparison of their coordination behavior with anions is also described by crystallographic and solution state experiments. The crystal structure demonstrates various types of spatial orientations of tripodal arms in two receptors and concomitantly interacts with anions distinctively. Intramolecular H-bonding between amide N–H and CO prevents opening of the receptor cavity in the crystal, which leads to a locked conformation of L1 having C(3v) symmetry and makes amide hydrogen unavailable for the anion which results in side cleft anion binding. However, in L2 we conveniently shift the anion binding sites to a distant position which increases cavity size as well as rules out any intramolecular H-bonding between amide N–H and CO. The crystal structure shows a different orientation of the arms in L2; it adopts a quasi-planar arrangement with C(2v) symmetry. In the crystal structure two arms are pointed in the same direction and while extending the contact the third arm is H-bonded with the apical N-atom through a –CN group, making a pseudo capsular cavity where the anion interacts. Most importantly spatial reorientation of the receptor L2 from a C(2v) symmetry to a folded conformation with a C(3v) symmetry was observed only in the presence of an octahedral SiF6(2-) anion and forms a sandwich type complex. Receptors L1 and L2 are explored for their solution state anion binding abilities. The substantial changes in chemical shifts were observed for the amide (-NH) and aromatic hydrogen (-CH) (especially for F(-)), indicating the role of these hydrogens in anion binding. The anion interacts with receptor L2 more strongly than L1 as confirmed by 1H NMR titration upon monitoring the -NH signal.

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Anion-Templated Syntheses of Rhombohedral Silver-Alkynyl Cage Compounds

Cited by 248 publications

References 74 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

Molecular and Crystal Structure of Chlorido[2-(N,N,N',N'- tetramethylamidinio)ethynido]silver

Anion complexation with cyanobenzoyl substituted first and second generation tripodal amide receptors: crystal structure and solution studies

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