Structural characterisation of two crystalline modifications of [Au9{P(C6H4OMe-p)3}8](NO3)3: the first example of skeletal isomerism in metal cluster chemistry

Briant, Clive E.; Hall, Kevin P.; Mingos, D. Michael P.

doi:10.1039/c39840000290

Cited by 68 publications

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“…This crown structure has already been observed for other Au 9 clusters. [Au 9 (P(p-C 6 H 4 OMe) 3 ) 8 ](NO 3 ) 3 can be crystallized in two skeletal isomers, the crown and the butterfly structure [10], whereas [Au 9 (PPh 3 ) 8 ](NO 3 ) 3 prefers the butterfly conformation in the solid state [9]. The radial Au-Au distances (2.617(11) and 2.681(12)Å) are shorter then the peripheral distances (2.776(13) and 2.802(13)Å), and the Au-P distances amount to 2.12(8) and 2.30(8)Å.…”

Section: Diffraction Results On the Core Structure And Elemental Compmentioning

confidence: 99%

“…For instance, well-formed crystals of [Au 9 (PPh 3 ) 8 ](NO 3 ) 3 can be obtained reliably by reducing [Au(PPh 3 )NO 3 ] with NaBH 4 in ethanol, followed by purification and crystallization from diluted solutions [9]. The cluster cation [Au 9 (PPh 3 ) 8 ] 3+ can be crystallized in two conformations of the gold polyhedron, the so-called crown structure and the butterfly structure [10,11]. It was found that [Au 9 (PPh 3 ) 8 ](NO 3 ) 3 in its butterfly conformation shows luminescence in the near infrared (NIR) in the solid state, which is advantageous for biomedical imaging [9].…”

Section: Introductionmentioning

confidence: 99%

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Isolation, Optical Properties and Core Structure of a Water-soluble, Phosphine-stabilized [Au₉]³⁺ Cluster

Gutrath¹,

Merkens

Schiefer

et al. 2013

Zeitschrift Für Naturforschung B

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A water-soluble, crystalline Au 9 cluster compound stabilized with sodium (m-sulfonatophenyl)diphenylphosphine (TPPMSNa) was obtained during the NaBH 4 reduction of [Au(TPPMSNa)Cl]·H 2 O in ethanol. Characterization by optical extinction spectroscopy, singlecrystal X-ray diffraction in combination with energy dispersive X-ray diffraction led to the preliminary formula Na (8−x) [Au 9 (TPPMS) 8 ]Cl (3−x) · nH 2 O (0 ≤ x ≤ 3, n ≈ 16) with the cluster core in crown conformation. 31 P{ 1 H} nuclear magnetic resonance spectroscopy revealed one singlet at 57.3 ppm. This is the first example where gold clusters stabilized by TPPMSNa formed crystals which where suitable for core structure determination.

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Section: Diffraction Results On the Core Structure And Elemental Compmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Isolation, Optical Properties and Core Structure of a Water-soluble, Phosphine-stabilized [Au₉]³⁺ Cluster

Gutrath¹,

Merkens

Schiefer

et al. 2013

Zeitschrift Für Naturforschung B

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“…Structural characterization of Au 9 3+ clusters was successful only by the employment of para-substituted ligands. [10][11][12] In the solid state, two skeletal isomers of [Au 9 (PR 3 )] 3+ clusters were found; in solution the clusters undergo fast rearrangements.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Intercluster Compounds Consisting of Gold Clusters and Keggin Anions

Schulz‐Dobrick

Jansen

2006

Eur J Inorg Chem

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“…Other modifications to the reaction conditions of the Brust-Schiffrin method, such as a reduction temperature of À78 C and the use of a hyperexcess of hexanethiol, results in an Au 38 (thiolate) 24 , based on TEM observations, LDI-TOF mass spectrometry, TGA analysis and elemental analysis [69]. The influence of preparation temperature on the size and monodispersity of dodecylthiol monolayer protected gold clusters has also been reported.…”

Section: Monolayer Protected Clustersmentioning

confidence: 99%

“…These Au 38 (PhCH 2 CH 2 S) 24 MPCs undergo place exchange reactions with other thiolate ligands or even PPh 3 ligand [71,72]. These Au 38 (PhCH 2 CH 2 S) 24 MPCs undergo place exchange reactions with other thiolate ligands or even PPh 3 ligand [71,72].…”

Section: Monolayer Protected Clustersmentioning

confidence: 99%

Gold Nanomaterials

Fernndez¹,

Monge²

2008

Modern Supramolecular Gold Chemistry

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The strong development of activities related to the nanoscience and nanotechnology of gold has led to a great number of publications in this research field. In this chapter, we will focus on the synthesis of cluster aggregates displaying gold-gold bonds and the formation of gold nanoparticles. Special consideration will be given to the chemical bottom-up approach for the synthesis of gold nanomaterials using different methods.Section 3.2 describes the synthesis and structure of small gold clusters taking into account the number of gold atoms, the reducing agents employed and the stabilizing ligands used, such as phosphines, arsines, thiols, and so on. Section 3.3 discusses the synthesis and properties of large size gold clusters such as the Au 55 cluster series. Finally, in Section 3.4, we describe the synthesis of gold nanoparticles and the development of new nanomaterials based on gold nanoparticles using bottom-up chemical methods and give a short summary of their properties and applications. Molecular Gold ClustersHerein we describe the synthesis and characterization of small-size homonuclear gold cluster compounds with a nuclearity ranging from 3 to 39 gold atoms. These types of clusters are usually characterized through definitive structural techniques such as single-crystal X-ray diffraction, enabling in-depth study of the structural arrangements found in the solid state.This section is divided into two main subsections. The first describes the synthesis and characterization of phosphine-stabilized gold clusters. The second focuses on the synthesis and characterization of thiol-stabilized gold clusters and the study of other stabilizers such as arsines or boranes are described.The first tetranuclear gold clusters were reported in the 1980s, namely [Au 4 (PPh 3 ) 4 (m-I) 2 ] (Au-Au distances from 2.649(1) to 2.828(1) Å) [1] and [Au 4 (dppm) 3 (m 3 -I)I] (Au-Au distances from 2.724(1) to 2.947(1) Å) [2]. The first cluster was prepared through a degradation reaction of the nonanuclear cluster [Au 9 (PPh 3 ) 8 ] 3þ , while the second was obtained by reaction of the already mentioned [Au 4 (PPh 3 ) 4 (m-I) 2 ] cluster and one equivalent of dppm ligand. Both structures display distorted tetrahedral cores of gold atoms with the iodine atoms bridging two different gold centers in the first case and three gold centers in the second (Scheme 3.1).In the 1990s, tetranuclear gold clusters [Au 4 (PR 3 ) 4 ]BF 4 (R ¼ t Bu [3] and (C 6 H 3 Me-1,3,5) [4]) were reported. Both clusters are synthesized from the corresponding oxonium salts [O{Au(PR 3 )] 3 ]BF 4 and [HO{Au(PR 3 )] 2 ]BF 4 (R ¼ t Bu and (C 6 H 3 Me-1,3,5)). In both clusters, X-ray diffraction analysis showed that gold atoms form a regular tetrahedron and each phosphine ligand is coordinated to one gold center (Scheme 3.2).The latest examples of tetranuclear gold clusters are based on phosphinocarborane ligands, namely [Au 4 {(PPh 2 ) 2 C 2 B 9 H 10 } 2 {P(4-OMeC 6 H 4 ) 3 } 2 ] [5] and, more recently, [Au 4 {(PPh 2 ) 2 C 2 B 9 H 10 } 2 {PPh 3 } 2 ] [6]. The firs...

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Structural characterisation of two crystalline modifications of [Au9{P(C6H4OMe-p)3}8](NO3)3: the first example of skeletal isomerism in metal cluster chemistry

Cited by 68 publications

References 0 publications

Isolation, Optical Properties and Core Structure of a Water-soluble, Phosphine-stabilized [Au₉]³⁺ Cluster

Isolation, Optical Properties and Core Structure of a Water-soluble, Phosphine-stabilized [Au₉]³⁺ Cluster

Supramolecular Intercluster Compounds Consisting of Gold Clusters and Keggin Anions

Gold Nanomaterials

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Structural characterisation of two crystalline modifications of [Au9{P(C6H4OMe-p)3}8](NO3)3: the first example of skeletal isomerism in metal cluster chemistry

Cited by 68 publications

References 0 publications

Isolation, Optical Properties and Core Structure of a Water-soluble, Phosphine-stabilized [Au9]3+ Cluster

Isolation, Optical Properties and Core Structure of a Water-soluble, Phosphine-stabilized [Au9]3+ Cluster

Supramolecular Intercluster Compounds Consisting of Gold Clusters and Keggin Anions

Gold Nanomaterials

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Product

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Isolation, Optical Properties and Core Structure of a Water-soluble, Phosphine-stabilized [Au₉]³⁺ Cluster

Isolation, Optical Properties and Core Structure of a Water-soluble, Phosphine-stabilized [Au₉]³⁺ Cluster