Self-assembly of new three-dimensional molecular architectures constructed from silver(i)–hexamethylenetetramine layers with supramolecular interactions

Zheng, Shao‐Liang; Tong, Ming‐Liang; Chen, Xiaoming; Ng, Seik Weng

doi:10.1039/b106925j

Cited by 48 publications

(5 citation statements)

References 32 publications

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“…The homoligand species for M = Ag and n = 1−2 have been considered in detail by us 9 and by others; ,− mixed-ligand species have been considered by Fox et al, and homoligand Cu species have also been studied. ,− On the basis of these results and other high-level calculations 17 for Au + (NH 3 ), the computational methods appear to overestimate the metal−ligand bond length by about 0.03 Å. As shown in Table , X-ray structural data − for species of the form Ag + (NH 3 ) 2 confirm this.…”

Section: Resultsmentioning

confidence: 99%

Explanation of the Anomalous Complexation of Silver(I) with Ammonia in Terms of the Poor Affinity of the Ion for Water

2004

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Silver(I) complexes with ammonia show the anomalous property that in aqueous solution the second association constant is larger than the first. This effect is known not to arise from gas-phase energetic effects or from any known mechanism through which similar anomalous behavior has been observed for other systems. Using density-functional theory (DFT) calculations for the inner-shell gas-phase complexes of Cu(I), Ag(I), and Au(I) with ammonia and/or aquo ligands, we conclude that the anomalous behavior of Ag(I) arises from its poor affinity for the solvent. Addition of the first ammonia results in the exclusion of not one but two water molecules from the inner solvation shell, selectively reducing the equilibrium constant for the first association. This is a strong specific solvation effect that cannot be described using dielectric continuum models of solvation.

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Section: Resultsmentioning

confidence: 99%

Explanation of the Anomalous Complexation of Silver(I) with Ammonia in Terms of the Poor Affinity of the Ion for Water

2004

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“…In the design and synthesis of metal−oorganic complexes, diphenic acid (H 2 dpa) is an excellent aromatic dicarboxylic ligand, in which two phenyl rings are not coplanar with each other owing to the steric hindrance of 2,2‘-positioned carboxylate groups in the coordination process. The distortion of the diphenyl spacer about the central bond can result in formation of discrete complexes and infinite polymers in the course of assembly with metal ions. − Meanwhile, hexamethylenetetramine (hmt) is another candidate for the neutral bridging ligand, which can adopt a potential terminal, μ 2 -, μ 3 -, or μ 4 -bridging mode; − moreover, hmt can act as an acceptor of a hydrogen bond to generate hydrogen bonding networks . The combination of dpa, hmt, and metal ions can produce some unique frameworks with beautiful aesthetics and useful properties.…”

Section: Introductionmentioning

confidence: 99%

Anion Effect on the Structural Conformation of Tetranuclear Cadmium(II) Complexes

Wang

Yuan

Jiang

et al. 2006

Crystal Growth & Design

102

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Six tetranuclear cadmium(II) complexes, Na[Cd 4 (hmt) 2 (H 2 O) 6 (dpa) 4 (NO 3 )]‚8H 2 O (1), Na [Cd 4 (hmt) hexamethylenetetramine, H 2 dpa ) diphenic acid), were synthesized by reactions of H 2 dpa, hmt, and CdX 2 (X ) NO 3 -, I -, Br -, Cl -, SCN -, and OAc -). All the complexes contain a basic unit [Cd 4 -(dpa) 4 ], in which four dpa ligands in a chelating bis-bidentate coordination mode link two six-coordinate and two seven-coordinate cadmium(II) centers. The research result demonstrates that the nature of the counterions has an important effect on the assembly process of neutral and anionic mixed ligands with metal ions. In 1-3, NO 3 -, I -, or Brbridges the two seven-coordinate Cd II centers of the unit to form a discrete tetranuclear molecule with a cis-conformation and hmt as a terminal ligand coordinated to each of the two six-coordinate cadmium(II) centers. Two SCNin 4 acting as terminal ligands generate a discrete trans-conformational tetranuclear cluster anion. The hmt in 5 acting as a µ-ligand links cis-conformational tetranuclear units by Cd-N bonds to generate a one-dimensional chain structure, while the hmt in 6 acting as a µ-ligand links the tetranuclear units by Cd-N bonds to generate a two-dimensional layer structure composed of a planar-conformation [Cd 4 (dpa) 4 ] unit. The fluorescent studies in the solid at room temperature show that the six complexes exhibit strong violet or blue emissions in the range 370-500 nm arising from the chargetransfer transition and that the bridging anions have a significant effect on their fluorescent properties.

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“…On the other hand, a linear bisamminesilver(I) complex is expected to dominate strongly in aqueous ammonia solutions because the third complex is very weak (Figure ). The crystal structures of [Ag(NH 3 ) 2 ][Ag(NO 2 ) 2 ], [Ag(NH 3 ) 2 ]NO 3 , [Ag(NH 3 ) 2 ] 2 SO 4 , [Ag(NH 3 ) 2 ]ClO 4 , catena-(bis(μ 3 -hexamethylenetetraamine)disilver(I) bis(bisamminesilver(I)) 1,2,4,5,-benzenetetracarboxylate trihydrate, and bis(bisamminesilver(I)) bis(biuretato- N , N ‘)nickel(II) hexahydrate all contain a linear bisamminesilver(I) complex with mean Ag−N bond distances of 2.115, 2.15(2), 2.110(3), 2.11−2.16 (two different phases at ambient and low temperature), 2.121, and 2.122 Å, respectively. The mean Ag−N bond distance in an aqueous ammonia solution of silver(I) nitrate, where the bisamminesilver(I) complex is strongly dominating, is reported from a large-angle X-ray scattering (LAXS) study to be 2.22(2) Å .…”

Section: Introductionmentioning

confidence: 99%

Coordination Chemistry of the Solvated Ag^I and Au^I Ions in Liquid and Aqueous Ammonia, Trialkyl and Triphenyl Phosphite, and Tri-n-butylphosphine Solutions

2006

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The coordination chemistry of solvated Ag(I) and Au(I) ions has been studied in some of the most strong electron-pair donor solvents, liquid and aqueous ammonia, and the P donor solvents triethyl, tri-n-butyl, and triphenyl phosphite and tri-n-butylphosphine. The solvated Ag(I) ions have been characterized in solution by means of extended X-ray absorption fine structure (EXAFS), Raman, and (107)Ag NMR spectroscopy and the solid solvates by means of thermogravimetry and EXAFS and Raman spectroscopy. The Ag(I) ion is two- and three-coordinated in aqueous and liquid ammonia solutions with mean Ag-N bond distances of 2.15(1) and 2.26(1) A, respectively. The crystal structure of [Ag(NH3)3]ClO4.0.47 NH3 (1) reveals a regular trigonal-coplanar coordination around the Ag(I) ion with Ag-N bond distances of 2.263(6) A and a Ag...Ag distance of 3.278(2) A separating the complexes. The decomposition products of 1 have been analyzed, and one of them, [Ag(NH3)2]ClO4, has been structurally characterized by means of EXAFS, showing [Ag(NH3)2] units connected into chains by double O bridges from perchlorate ions; the Ag...Ag distance is 3.01(1) A. The linear bisamminegold(I) complex, [Au(NH3)2]+, is predominant in both liquid and aqueous ammonia solutions, as well as in solid [Au(NH3)2]BF4, with Au-N bond distances of 2.022(5), 2.025(5), and 2.026(7) A, respectively. The solvated Ag(I) ions are three-coordinated, most probably in triangular fashion, in the P donor solvents with mean Ag-P bond distances of 2.48-2.53 A. The Au(I) ions are three-coordinated in triethyl phosphite and tri-n-butylphosphine solutions with mean Au-P bond distances of 2.37(1) and 2.40(1) A, respectively.

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Self-assembly of new three-dimensional molecular architectures constructed from silver(i)–hexamethylenetetramine layers with supramolecular interactions

Cited by 48 publications

References 32 publications

Explanation of the Anomalous Complexation of Silver(I) with Ammonia in Terms of the Poor Affinity of the Ion for Water

Explanation of the Anomalous Complexation of Silver(I) with Ammonia in Terms of the Poor Affinity of the Ion for Water

Anion Effect on the Structural Conformation of Tetranuclear Cadmium(II) Complexes

Coordination Chemistry of the Solvated Ag^I and Au^I Ions in Liquid and Aqueous Ammonia, Trialkyl and Triphenyl Phosphite, and Tri-n-butylphosphine Solutions

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Self-assembly of new three-dimensional molecular architectures constructed from silver(i)–hexamethylenetetramine layers with supramolecular interactions

Cited by 48 publications

References 32 publications

Explanation of the Anomalous Complexation of Silver(I) with Ammonia in Terms of the Poor Affinity of the Ion for Water

Explanation of the Anomalous Complexation of Silver(I) with Ammonia in Terms of the Poor Affinity of the Ion for Water

Anion Effect on the Structural Conformation of Tetranuclear Cadmium(II) Complexes

Coordination Chemistry of the Solvated AgI and AuI Ions in Liquid and Aqueous Ammonia, Trialkyl and Triphenyl Phosphite, and Tri-n-butylphosphine Solutions

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Coordination Chemistry of the Solvated Ag^I and Au^I Ions in Liquid and Aqueous Ammonia, Trialkyl and Triphenyl Phosphite, and Tri-n-butylphosphine Solutions