三苯基膦：转换硫醇保护的纳米粒子成[Au25(PPh3)10(SR)5Cl2]2+

doi:10.3866/PKU.WHXB201710091

Abstract

Abstract:

Research on gold nanoclusters is at the frontier of nanoscience and nanotechnology. The introduction of the first phosphine-protected gold nanocluster, Au₁₁(PPh₃)₇(SCN)₃ (where PPh₃ stands for triphenylphosphine and Ph stands for benzene), can be dated back to 1969. As research in the field progressed, many structures of phosphine-protected nanoclusters such as Au₅, Au₈, Au₁₃, and Au₃₉ were reported. However, the stability of these phosphine-protected nanoclusters was not satisfactory, which handicapped their research and application. In an attempt to find alternatives for phosphine-protected nanoclusters, thiolated gold nanoclusters have attracted extensive attention in recent years. So far, there has been great progress primarily owing to the development of wet-chemical synthesis techniques, among which the utilization of ligand-exchange has been proved to be very effective to synthesize thiolated gold nanoclusters. It can be easily understood that phosphine in gold nanoclusters can be exchanged with thiolate because the latter has stronger affinity for gold. However, we recently found that the reverse ligand-exchange, i.e., the exchange of thiolate with phosphine, can also take place. Some questions have naturally arisen: Is the reverse ligand-exchange only applicable to superatomic [Au₂₅(SR)₁₈]⁻ (SR: thiolate) nanoclusters? Can it occur in other thiolated gold nanoclusters? If so, is this reverse ligand-exchange also dependent on the starting nanoclusters? These intriguing issues have inspired us to conduct this work.

We investigated the reactions of PPh₃ with some thiolated gold nanoparticles, including [Au₂₃(SC₆H₁₁)₁₆]⁻, Au₂₄(SC₂H₄Ph)₂₀, Au₃₆(TBBT)₂₈ (where TBBT stands for 4-(tert-butyl) benzene-1-thiolate), Au₃₈(SC₂H₄Ph)₂₀, mixed nanoclusters, and 3 nm Au nanoparticles. Surprisingly, the experimental results showed that under the action of PPh₃, thiolated gold nanoclusters (or nanoparticles) with different compositions, structures, sizes, and protecting thiolates can be uniformly transformed to [Au₁₁(PPh₃)₈Cl₂]⁺ and then [Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺. In other words, PPh₃ is a universal converter for these thiolated gold nanoparticles. However, gold nanoparticles that are protected by polyvinylpyrrolidone (PVP) or citrate and [Ag₂₅(SPhMe₂)₁₈]⁻ particles cannot be transformed to [Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺ and [Ag₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺, respectively, under the same conditions, which indicated that the special reactivity with PPh₃ is unique to thiolated gold nanoparticles. Our preliminary investigation on a possible reaction path between thiolated gold nanoparticles and PPh₃ also revealed that the peeling process found in Au₂₅ nanoclusters may be applicable to the conversion of [Au₂₃(SC₆H₁₁)₁₆]⁻, but not other nanoclusters like Au₂₄(SC₂H₄Ph)₂₀ and Au₃₆(TBBT)₂₈.

Employing this special chemistry, we synthesized seven [Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺ species with various ligands and investigated the effect of the ligand on the luminescence properties of [Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺. We found that the luminescence quantum yields decreased in the following order: [Au₂₅(PPh₃)₁₀(SCH₂Ph-t-Bu)₅Cl₂]²⁺ (1.32 × 10⁻⁴) > [Au₂₅(PPh₃)₁₀(SCH₂Ph)₅Cl₂]²⁺ (8.23 × 10⁻⁵) > [Au₂₅(PPh₃)₁₀(SC₂H₄Ph)₅Cl₂]²⁺ (5.35 × 10⁻⁶) > [Au₂₅(PPh₃)₁₀(SC₁₂H₂₅)₅Cl₂]²⁺ (5.02 × 10⁻⁶) > [Au₂₅(PPh₃)₁₀(SPh-t-Bu)₅Cl₂]²⁺ (3.97 × 10⁻⁶) > [Au₂₅(PPh₃)₁₀(SC₆H₁₃)₅Cl₂]²⁺ (3.73 × 10⁻⁶) > [Au₂₅(PPh₃)₁₀(S-c-C₆H₁₁)₅Cl₂]²⁺ (1.53 × 10⁻⁶). Therefore, it can be concluded that SCH₂Ph-t-Bu is the best ligand, while S-c-C₆H₁₁ is the worse one for triggering luminescence from gold nanoparticles in the investigated thiolates.

Since such diversity in surface ligands is not found in other nanoclusters (e.g., [Au₂₅(SR)₁₈]⁻), the special chemistry between thiolated gold nanoparticles and PPh₃ provides excellent opportunities to investigate the effect of ligands on the properties of gold nanoparticles and to screen ligands for special applications.

In summary, in this work we reveal the unique chemistry of thiolated gold nanoparticles with PPh₃ and provide excellent opportunities for investigating ligand effects of gold nanoparticles and screening ligands for special applications.

Key words: Thiolated gold nanoparticles, PPh₃, Universal converter, Luminescence

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Min ZHU,Manbo LI,Chuanhao YAO,Nan XIA,Yan ZHAO,Nan YAN,Lingwen LIAO,Zhikun WU. PPh_3: Converts Thiolated Gold Nanoparticles to [Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺[J].Acta Phys. -Chim. Sin., 2018, 34(7): 792-798.

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PPh_3: Converts Thiolated Gold Nanoparticles to [Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺

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PPh_3: Converts Thiolated Gold Nanoparticles to [Au₂₅(PPh₃)₁₀(SR)₅Cl₂]²⁺