Mixed‐Metal‐Gold Phosphine Cluster Compounds

Mueting, Ann M.; Alexander, Bruce D.; Boyle, P. D.; Casalnuovo, A. L.; Ito, Larry N.; Johnson, Brian J.; Pignolet, L. H.; Leeaphon, Malee; Meyer, Karsten; Walton, Richard A.; Heinekey, D. Michael; Harper, T. Gregory P.

doi:10.1002/9780470132609.ch63

Cited by 18 publications

(8 citation statements)

References 25 publications

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“…The solid product (∼130 mg) was obtained by evaporating the solvent. [Au 9 (PPh 3 ) 8 ](NO 3 ) 3 was synthesized by a method similar to those in the literature. , NaBH 4 (0.48 mmol) dissolved in ethanol (23 mL) was added dropwise into Au(PPh 3 )(NO 3 ) (1.0 g, 1.9 mmol, prepared according to the literature) dispersed in ethanol (40 mL). After 2 h of stirring at room temperature, the reaction mixture was filtrated.…”

Section: Methodsmentioning

confidence: 99%

Suppressing Isomerization of Phosphine-Protected Au₉ Cluster by Bond Stiffening Induced by a Single Pd Atom Substitution

et al. 2017

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The fluxional nature of small gold clusters has been exemplified by reversible isomerization between [Au(PPh)] with a crown motif (Au(C)) and that with a butterfly motif (Au(B)) induced by association and dissociation with compact counteranions (NO, Cl). However, structural isomerization was suppressed by substitution of the central Au atom of the Au core in [Au(PPh)] with a Pd atom: [PdAu(PPh)] with a crown motif (PdAu(C)) did not isomerize to that with a butterfly motif (PdAu(B)) upon association with the counteranions. Density functional theory calculation showed that the energy difference between PdAu(C) and PdAu(B) is comparable to that between Au(C) and Au(B), indicating that the relative stabilities of the isomers are not a direct cause for the suppression of isomerization. Temperature dependence of Debye-Waller factors obtained by X-ray absorption fine-structure analysis revealed that the intracluster bonds of PdAu(C) were stiffer than the corresponding bonds in Au(C). Natural bond orbital analysis suggested that the radial Pd-Au and lateral Au-Au bonds in PdAu(C) are stiffened due to the increase in the ionic nature and decrease in electrostatic repulsion between the surface Au atoms, respectively. We conclude that the formation of stiffer metal-metal bonds by Pd atom doping inhibits the isomerization from PdAu(C) to PdAu(B).

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Section: Methodsmentioning

confidence: 99%

Suppressing Isomerization of Phosphine-Protected Au₉ Cluster by Bond Stiffening Induced by a Single Pd Atom Substitution

et al. 2017

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“…All commercially available reagents were used as received. Au(PPh 3 )(NO 3 ) (ref ) was synthesized from AuCl(PPh 3 ) obtained from chloroauric acid tetrahydrate . AgCl(PPh 3 ) and CuCl(PPh 3 ) were synthesized from silver nitrate and copper chloride dihydrate, respectively .…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Trimetallic (HPd@M₂Au₈)³⁺ Superatoms (M = Ag, Cu) via Hydride-Mediated Regioselective Doping to (Pd@Au₈)²⁺

2019

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We have recently reported that hydride (H – ) doped superatom (HPd@Au 8 ) + protected by eight PPh 3 ligands selectively grew into (HPd@Au 10 ) 3+ by the nucleophilic addition of two Au(I)Cl units. In the present study, (HPd@Au 8 ) + was successfully converted to unprecedented trimetallic (HPd@M 2 Au 8 ) 3+ superatoms (M = Ag, Cu) by controlled doping of two Ag(I)Cl or Cu(I)Cl units, respectively. Single-crystal X-ray diffraction analysis demonstrated that two Ag(I) or Cu(I) ions were regioselectively incorporated. Theoretical calculations suggested that hydrogens in (HPd@M 2 Au 8 ) 3+ (M = Au, Ag, Cu) occupy the same bridging site between the central Pd atom and the surface Au atom. (HPd@Ag 2 Au 8 ) 3+ exhibited photoluminescence at 775 nm, with the enhanced quantum yield of 0.09%, although it is structurally and electronically equivalent with (HPd@Au 10 ) 3+ . This study demonstrates that hydride-mediated growth process is a promising atomically-precise bottom-up synthetic method of new multimetallic superatoms.

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“…Au 9 Cluster Preparation: According to ref 8a,. NaBH 4 (0.018 g, 0.48 mmol) in ethanol (23 mL) was added dropwise into Au(PPh 3 )NO 3 (1.0 g, 1.9 mmol, prepared according to literature18) in ethanol (40 mL) whilst stirring. The mixture was stirred at room temperature for 2 h and then filtered.…”

Section: Methodsmentioning

confidence: 99%

Crystal Structure, Electrochemical and Optical Properties of [Au₉(PPh₃)₈](NO₃)₃

et al. 2007

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Mixed‐Metal‐Gold Phosphine Cluster Compounds

Cited by 18 publications

References 25 publications

Suppressing Isomerization of Phosphine-Protected Au₉ Cluster by Bond Stiffening Induced by a Single Pd Atom Substitution

Suppressing Isomerization of Phosphine-Protected Au₉ Cluster by Bond Stiffening Induced by a Single Pd Atom Substitution

Synthesis of Trimetallic (HPd@M₂Au₈)³⁺ Superatoms (M = Ag, Cu) via Hydride-Mediated Regioselective Doping to (Pd@Au₈)²⁺

Crystal Structure, Electrochemical and Optical Properties of [Au₉(PPh₃)₈](NO₃)₃

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Mixed‐Metal‐Gold Phosphine Cluster Compounds

Cited by 18 publications

References 25 publications

Suppressing Isomerization of Phosphine-Protected Au9 Cluster by Bond Stiffening Induced by a Single Pd Atom Substitution

Suppressing Isomerization of Phosphine-Protected Au9 Cluster by Bond Stiffening Induced by a Single Pd Atom Substitution

Synthesis of Trimetallic (HPd@M2Au8)3+ Superatoms (M = Ag, Cu) via Hydride-Mediated Regioselective Doping to (Pd@Au8)2+

Crystal Structure, Electrochemical and Optical Properties of [Au9(PPh3)8](NO3)3

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Suppressing Isomerization of Phosphine-Protected Au₉ Cluster by Bond Stiffening Induced by a Single Pd Atom Substitution

Suppressing Isomerization of Phosphine-Protected Au₉ Cluster by Bond Stiffening Induced by a Single Pd Atom Substitution

Synthesis of Trimetallic (HPd@M₂Au₈)³⁺ Superatoms (M = Ag, Cu) via Hydride-Mediated Regioselective Doping to (Pd@Au₈)²⁺

Crystal Structure, Electrochemical and Optical Properties of [Au₉(PPh₃)₈](NO₃)₃