The Phosphine‐Stabilized Gold–Arsenic Clusters [Au19(AsnPr)8(dppe)6]Cl3, [Au10(AsnPr)4(dppe)4]Cl2, [Au17(AsnPr)6(As2nPr2)(dppm)6]Cl3, and [Au10(AsPh)4(dppe)4]Cl2: Synthesis, Characterization, and DFT Calculations

Sevillano, Paloma; Fuhr, Olaf; Kattannek, Marco; Nava, Paola; Hampe, Oliver; Lebedkin, Sergej; Ahlrichs, Reinhart; Fenske, Dieter; Kappes, Manfred M.

doi:10.1002/anie.200504566

Cited by 38 publications

(16 citation statements)

References 66 publications

(26 reference statements)

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“…179 Au 38 clusters with phosphine or thiolate ligands were calculated to develop molecular gold-thiolate rings on their surface. 180 Various, open-structured, phosphine-stabilized gold-arsenic clusters were synthesized and theoretically modelled by Sevillano et al 181 For earlier work on Au 28 (SMe) 16 and Au 38 (SMe) 24 , including their chirality aspects, recall Garzo´n et al 182 The corresponding optical activity had earlier been seen in glutathione-passsivated gold nanoclusters in the 20-40 gold atom range.…”

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confidence: 99%

Theoretical chemistry of gold. III

2008

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Section: àmentioning

confidence: 99%

Theoretical chemistry of gold. III

2008

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“…For instance, Fackler et al and Fenske et al recently reported the structural characterization and luminescence of molecules with arsenic or phosphorus donor ligands containing between nine and nineteen gold centers [50][51][52]. However, in selected examples where the ligands had several donor centers, or when these could act as donors to more than one gold center, the molecules displayed a larger number of gold atoms and, usually, the aggregation occurred inside the molecules.…”

Section: Network From Higher Nuclearity Systemsmentioning

confidence: 99%

Luminescence of Supramolecular Gold‐Containing Materials

López‐de‐Luzuriaga

2008

Modern Supramolecular Gold Chemistry

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In addition to the characteristics that make gold a unique element, such as the lowest electrochemical potential of all metals, its high electronegativity, or the fact that it may have a mononegative oxidation state, perhaps the most intriguing characteristic is the tendency of many gold complexes to aggregate into oligomers or supramolecular assemblies through metal-metal interactions. This fact, far from being a chemical curiosity, has become an object of study because of the associated properties. One of the most studied properties and that which involves many groups all over the world is the luminescence displayed by many gold-containing complexes. In fact, after the discovery of the luminescence of the three-coordinate complex [AuCl(PPh 3 ) 2 ] by Dori and coworkers in 1970 [1], the number of groups that have studied this topic has increased rapidly in recent years, together with the number of synthesized luminescent gold molecules. At the same time, the large number of studies performed in this area has provided knowledge of the conditions that gold complexes require to display luminescence. For instance, luminescence can originate from ligands, assigned to certain geometries around the gold atom or from the presence of metal-metal interactions in the complexes. More specifically, it can be produced by transitions between orbitals of the metal center exclusively, in orbitals of the ligands, usually among p orbitals, or in transitions involving both metal and ligands, where these can act as donors or acceptors of electronic density (charge transfer transitions). In gold (I), with a d 10 closed shell configuration, the ground state is 1 S 0 , while the excited states are 3 D 2 , 3 D 1 , 3 D 0 and 1 D 0 (see Figure 6.1) [2].Of all these, the only permitted electronic transition is 1 D 0 1 S 0 , while the rest are forbidden according to the spin rule, leading to phosphorescent emissions. However, these are precisely the ones responsible for the emissions found in many luminescent gold complexes, appearing in a range between 500 and 700 nm (665 nm in the gaseous ion). j347Another very important factor that should be considered is the expected large spin-orbit effect promoted by a heavy atom such as gold. This effect produces a relaxation of the spin rule and makes orbital forbiddenness instead of the spin rule the key factor for determining whether a gold complex will show luminescence. For instance, phosphorescence is generally not observed for linear molecules (where the ligands are not involved in the transitions), since the mixing of s, p z and d z 2 of gold form a HOMO of S þ symmetry, while the LUMO orbital is formed mainly from p x and p y leading to a P symmetry, consequently, there is no orbital forbiddenness in the transition and phosphorescence is not observed [3]. Another possible coordination environment at gold is the tetrahedral one. In that case, the HOMO and the LUMO are 1 T 2 in symmetry and the transition is allowed according to Laportes rule; therefore, phosphorescence is not observed in thes...

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“…Mass spectrometric techniques have been proven to be very useful for elucidation of atomic compositions of large inorganic cluster molecules such as [Ag 26 In 18 S 36 Cl 6 (dppm) 10 (thf ) 4 ] 2+22 and [Au 19 (As n Pr) 8 (dppe) 6 ] 3+ . 24 The ESI-TOF mass spectra of DMF solutions of 2 in negative-ion mode are shown in Fig. 3 and are dominated by one peak of the singly charged cluster anion [Cu 19 S 28 (SnPh) 12 ] − at m/z 4454.17 (Table 3).…”

Section: Mass Spectrometrymentioning

confidence: 99%

A ternary Cu–Sn–S cluster complex—(NBu4)[Cu19S28(SnPh)12(PEt2Ph)3]

et al. 2012

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Reaction of a mixture of CuCl, PhSnCl(3) and PEt(2)Ph with S(SiMe(3))(2) in THF resulted initially in the unexpected synthesis of the ionic, mixed copper-tin sulfide cluster [Li(thf)(4)][Cu(19)S(28)(SnPh)(12)(PEt(2)Ph)(3)] in low yields. However, by adding NBu(4)Cl to the reaction solutions we were able to selectively synthesize the structurally similar cluster ion in (NBu(4))[Cu(19)S(28)(SnPh)(12)(PEt(2)Ph)(3)]. Structural characterization by single crystal X-ray analysis reveals that the cluster anions consist in principle of a copper sulfide core decorated by PhSn(3+) groups. Although additional phosphine ligands are attached to copper atoms the clusters possess an open 'Cu(3)S(3)' face mostly protected by the [Li(thf)(4)](+) and (NBu(4))(+) counterions in the crystal structure. The cluster (NBu(4))[Cu(19)S(28)(SnPh)(12)(PEt(2)Ph)(3)] displays near-infrared, temperature-dependent photoluminescence at ∼820-930 nm in the solid state, which is especially bright at temperatures below ∼100 K.

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The Phosphine‐Stabilized Gold–Arsenic Clusters [Au₁₉(AsnPr)₈(dppe)₆]Cl₃, [Au₁₀(AsnPr)₄(dppe)₄]Cl₂, [Au₁₇(AsnPr)₆(As₂nPr₂)(dppm)₆]Cl₃, and [Au₁₀(AsPh)₄(dppe)₄]Cl₂: Synthesis, Characterization, and DFT Calculations

Abstract: International audienc

Cited by 38 publications

References 66 publications

Theoretical chemistry of gold. III

Theoretical chemistry of gold. III

Luminescence of Supramolecular Gold‐Containing Materials

A ternary Cu–Sn–S cluster complex—(NBu4)[Cu19S28(SnPh)12(PEt2Ph)3]

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