Dynamic Diglyme-Mediated Self-Assembly of Gold Nanoclusters

Compel, W. Scott; Wong, O. Andrea; Chen, Xi; Yi, Chongyue; Geiss, Roy H.; Häkkinen, Hannu; Knappenberger, Kenneth L.; Ackerson, Christopher J.

doi:10.1021/acsnano.5b02850

Cited by 36 publications

(53 citation statements)

References 51 publications

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“…Metallophilic interactions3031323334 between the closed-shell Ag(I) and Au(I) centres that are present in the M 2 (SR) 3 staples of I and II , and π–π interactions between the aryl groups of the ligands, may also contribute to attractive forces between the two clusters. The sulfur atoms of monothiol ligands (DMBT and PET) involved in these reactions are bound to the metal atoms in the clusters, and these ligands do not have any other functional groups which are free to act as linker molecules between the clusters, unlike in the cases of a few previous reports3536. Moreover, we did not detect the presence of any extra DMBT or PET ligands in the adduct in mass spectrometric measurements, as in the case of clusters having different ligands37.…”

Section: Resultsmentioning

confidence: 97%

Structure-conserving spontaneous transformations between nanoparticles

Krishnadas¹,

Baksi²,

Ghosh³

et al. 2016

Nat Commun

114

186

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Ambient, structure- and topology-preserving chemical reactions between two archetypal nanoparticles, Ag25(SR)18 and Au25(SR)18, are presented. Despite their geometric robustness and electronic stability, reactions between them in solution produce alloys, AgmAun(SR)18 (m+n=25), keeping their M25(SR)18 composition, structure and topology intact. We demonstrate that a mixture of Ag25(SR)18 and Au25(SR)18 can be transformed to any arbitrary alloy composition, AgmAun(SR)18 (n=1–24), merely by controlling the reactant compositions. We capture one of the earliest events of the process, namely the formation of the dianionic adduct, (Ag25Au25(SR)36)2−, by electrospray ionization mass spectrometry. Molecular docking simulations and density functional theory (DFT) calculations also suggest that metal atom exchanges occur through the formation of an adduct between the two clusters. DFT calculations further confirm that metal atom exchanges are thermodynamically feasible. Such isomorphous transformations between nanoparticles imply that microscopic pieces of matter can be transformed completely to chemically different entities, preserving their structures, at least in the nanometric regime.

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Section: Resultsmentioning

confidence: 97%

Structure-conserving spontaneous transformations between nanoparticles

Krishnadas¹,

Baksi²,

Ghosh³

et al. 2016

Nat Commun

114

186

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“…In addition, its strong absorption at 380 nm is also similar to that in the two Au 11 clusters. The large shift of the 460 nm band in Au 22 (dppee) 7 relative to the ≈420 nm band in the Au 11 cluster suggests that the new Au 22 cluster core is unlikely to be a polymer or assembly of isolated dppee‐protected Au 11 units. The CID and NMR data to be presented below are consistent with these observations.…”

Section: Discussionmentioning

confidence: 99%

Polymorphism of Phosphine-Protected Gold Nanoclusters: Synthesis and Characterization of a New 22-Gold-Atom Cluster

Zhang

Williard

Wang

2016

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A new Au22 nanocluster, protected by bis(2-diphenyl-phosphino)ethyl ether (dppee or C28 H28 OP2 ) ligand, has been synthsized and purified with high yield. Electrospray mass spectrometry shows that the new cluster has a formula of Au22 (dppee)7 , containing 22 gold atoms and seven dppee ligands. The cluster is found to be stable as a solid, but metastable in solution. The new cluster has been characterized by UV-Vis-NIR absorption spectroscopy, collision-induced dissociation, and (31) P-NMR. The properties of the new cluster have been compared with the previous Au22 (dppo)6 nanocluster (dppo = 1,8-bis(diphenyl-phosphino)octane or C32 H36 P2 ), which contains two fused Au11 units. All the experimental data indicate that the new Au22 (dppee)7 cluster is different from the previously known Au22 (dppo)6 cluster and represents a new Au22 core, which contains most likely one Au11 motif with several Au2 (dppee) or Au(dppee) units. The Au22 (dppee)7 cluster provides a new example of the ligand effects on the nuclearity and structural polymorphism of phosphine-protected atom-precise gold nanoclusters.

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“…Furthermore, we show that emergence of plasmonic coupling can be studied using these MPC multimers. Previously, MPC dimers have been demonstrated using dynamic diglyme bonding 29 , however, in our approach, dithiol-bridged MPCs form a covalently bound system. The rest of the paper is structured as follows.…”

Section: Introductionmentioning

confidence: 96%

Covalently linked multimers of gold nanoclusters Au₁₀₂(p-MBA)₄₄and Au_∼250(p-MBA)_n

et al. 2016

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We present the synthesis, separation, and characterization of covalently-bound multimers of paramercaptobenzoic acid (p-MBA) protected gold nanoclusters. The multimers were synthesized by performing a ligand-exchange reaction of a pre-characterized Au 102 (p-MBA) 44 nanocluster with biphenyl-4,4'dithiol (BPDT). The reaction products were separated using gel electrophoresis yielding several distinct bands. The bands were analyzed by transmission electron microscopy (TEM) revealing monomer, dimer, and trimer fractions of the nanocluster. TEM analysis of dimers in combination with molecular dynamics simulations suggest that the nanoclusters are covalently bound via a disulfide bridge between BPDT molecules. The linking chemistry is not specific to Au 102 (p-MBA) 44 . The same approach yields multimers also for a larger monodisperse p-MBA-protected cluster of approximately 250 gold atoms, Au ∼250 (p-MBA) n . While the Au 102 (p-MBA) 44 is not plasmonic, the Au ∼250 (p-MBA) n nanocluster supports localized surface plasmon resonance (LSPR) at 530 nm. Multimers of the Au ∼250 (p-MBA) n exhibit additional transitions in their UV-vis spectrum at 630 nm and 810 nm, indicating the presence of hybridized LSPR modes. Well-defined structures and relatively small sizes make these systems excellent candidates for connecting ab initio theoretical studies and experimental quantum plasmonics. Moreover, our work opens new possibilities in the controlled synthesis of advanced monodisperse nanocluster superstructures. † Electronic supplementary information (ESI) available: Details of syntheses and purification; additional images of PAGE runs; mass spectrum of Au 102 ( p-MBA) 44 ; 1 H NMR spectra of clusters; TEM analysis of cluster sizes; additional TEM images; core-to-core distance and angle distributions from simulations; additional multimer size statistics; additional UV-vis spectra for Au ∼250 ( p-MBA) n multimers and aggregates. See

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Dynamic Diglyme-Mediated Self-Assembly of Gold Nanoclusters

Cited by 36 publications

References 51 publications

Structure-conserving spontaneous transformations between nanoparticles

Structure-conserving spontaneous transformations between nanoparticles

Polymorphism of Phosphine-Protected Gold Nanoclusters: Synthesis and Characterization of a New 22-Gold-Atom Cluster

Covalently linked multimers of gold nanoclusters Au₁₀₂(p-MBA)₄₄and Au_∼250(p-MBA)_n

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Dynamic Diglyme-Mediated Self-Assembly of Gold Nanoclusters

Cited by 36 publications

References 51 publications

Structure-conserving spontaneous transformations between nanoparticles

Structure-conserving spontaneous transformations between nanoparticles

Polymorphism of Phosphine-Protected Gold Nanoclusters: Synthesis and Characterization of a New 22-Gold-Atom Cluster

Covalently linked multimers of gold nanoclusters Au102(p-MBA)44and Au∼250(p-MBA)n

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Covalently linked multimers of gold nanoclusters Au₁₀₂(p-MBA)₄₄and Au_∼250(p-MBA)_n