Electronic conductivity of alkyne-capped ruthenium nanoparticles

Kang, Xiongwu; Chen, Shaowei

doi:10.1039/c2nr30213f

Cited by 30 publications

(43 citation statements)

References 37 publications

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“…As described previously, a significant shift in the C≡C stretch mode was observed on thiol binding to the gold surface indicating the significant electronic coupling between the benzenethiol and the surface. It is noteworthy that the C≡C stretch mode is so sensitive to temperature in this system, as also found in other reports on Raman of alkynes [37]. Their large polarizability renders them sensitive to electronic changes within their molecular vicinity, particularly in conjugated systems [40–41].…”

Section: Resultssupporting

confidence: 80%

“…The alkyne C≡C stretch mode, which is by far the most intense mode in the powder sample, is reduced in relative intensity in the 2D single-layer array, but remains a dominant feature albeit shifted from 2222 to 2211 cm −1 on surface binding. This suggests a modest weakening of the C≡C bond presumably induced by binding of the thiol to the surface [37]. By comparison, the Raman modes from the S-BPP moiety are weaker than the benzenethiol moiety in the SAM spectrum.…”

Section: Resultsmentioning

confidence: 99%

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The influence of molecular mobility on the properties of networks of gold nanoparticles and organic ligands

Devid¹,

Martinho²,

Kamalakar³

et al. 2014

Beilstein J. Nanotechnol.

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SummaryWe prepare and investigate two-dimensional (2D) single-layer arrays and multilayered networks of gold nanoparticles derivatized with conjugated hetero-aromatic molecules, i.e., S-(4-{[2,6-bipyrazol-1-yl)pyrid-4-yl]ethynyl}phenyl)thiolate (herein S-BPP), as capping ligands. These structures are fabricated by a combination of self-assembly and microcontact printing techniques, and are characterized by electron microscopy, UV–visible spectroscopy and Raman spectroscopy. Selective binding of the S-BPP molecules to the gold nanoparticles through Au–S bonds is found, with no evidence for the formation of N–Au bonds between the pyridine or pyrazole groups of BPP and the gold surface. Subtle, but significant shifts with temperature of specific Raman S-BPP modes are also observed. We attribute these to dynamic changes in the orientation and/or increased mobility of the molecules on the gold nanoparticle facets. As for their conductance, the temperature-dependence for S-BPP networks differs significantly from standard alkanethiol-capped networks, especially above 220 K. Relating the latter two observations, we propose that dynamic changes in the molecular layers effectively lower the molecular tunnel barrier for BPP-based arrays at higher temperatures.

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Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 99%

The influence of molecular mobility on the properties of networks of gold nanoparticles and organic ligands

Devid¹,

Martinho²,

Kamalakar³

et al. 2014

Beilstein J. Nanotechnol.

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show abstract

“…The particles exhibited a major absorption peak at around 200 nm ascribing to the p-p* electronic transitions of internal (sp 2 ) graphitic carbons. Figure 1 (b) responses the changes of carbon nanoparticle spectrum to the featureless exponential decay profile anticipating for nanosized Ru particles [15]. This suggested the success of the ruthenium deposition.…”

Section: Resultsmentioning

confidence: 93%

“…Recently, many reports have been generally successfully prepared alkyl vinylidene -linkage to ruthenium core using the special coordinating ligand for example terminal alkyne [1][2][3][4][5] or some vinyl aromatic [6][7]. It is confirmed that alkyne fragments around the metal core do not only functions as protecting ligands promoting the stability of the nanoparticles but also enhances some optical and fluorescence characteristic via the pi-bond interaction between methylene and metal core [8].…”

Section: Introductionmentioning

confidence: 87%

One-pot Synthesis of Octyne-Ruthenium on Carbon Nanoparticles

2017

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Abstract. The attempts to manipulate ruthenium nanoparticle by the passivation of π bonds linkage is of interest for many years. That is the way to enhance its optical properties and fluorescence characteristics which can promote the usage for sensor application. Other view, the usage of carbon nanoparticle is governed in many aspects including its fluorescence properties. Therefore, the combination between those two valued nanoparticles was set by conducting the simple synthesis method. With the as-prepared carbon nanoparticles, all other reagents (ruthenium (III) chloride, octyne and Sodium borohydride) were mixed in the same batch. The ratio of carbon substrate, ruthenium (III) chloride and octyne was 10: 1: 3. The particle yielded was then purified and subjected to characterize using some spectroscopy techniques including photoluminescence. The results showed that size of carbon particle before and after ruthenium deposition were 5.0 and 6.3 nanometers, respectively. Octyne was coordinated self-assembly on the ruthenium surface which was 8.1 nanometers in diameter. Moreover, octyne-protected ruthenium on carbon nanoparticles showed the remarkably increasing of fluorescence Intensity. Therefore, the functionalization of carbon nanoparticle with octyne-ruthenium can be a promising strategy to develop a novel complex of ruthenium.

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“…It should be noted that similar to ferrocenecarboxylatestabilized ruthenium nanoparticles reported in the previous study, 15 the binding energies of the Ru 3d electrons were somewhat higher than those of alkyne-capped ruthenium nanoparticles because the Ru−O bonds were far more polar than the Ru−C ones. 4 In addition, on the basis of the integrated peak areas, the molar ratio of the COO − carbon to the phenyl ring carbon was estimated to be 1:7.7, close to that (1:10) anticipated from the NAA molecular structure.…”

Section: Methodsmentioning

confidence: 99%

Chemical Reactivity of Naphthalenecarboxylate-Protected Ruthenium Nanoparticles: Intraparticle Charge Delocalization Derived from Interfacial Decarboxylation

Chen

Deming

et al. 2015

J. Phys. Chem. C

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Ruthenium nanoparticles were prepared by thermolytic reduction of RuCl 3 in 1,2-propanediol containing sodium 2-naphthalenecarboxylate. Transmission electron microscopic measurements showed that the average diameter of the resulting 2-naphthalenecarboxylate-protected ruthenium nanoparticles (RuCOONA) was 1.30 ± 0.27 nm. Interestingly, hydrothermal treatment of the nanoparticles at controlled temperatures led to decarboxylation at the metal−ligand interface, and the naphthalenyl moieties became directly bonded to the metal cores, which was confirmed by infrared and X-ray photoelectron spectroscopic measurements. In comparison with the as-produced RuCOONA nanoparticles, the decarboxylated nanoparticles (RuNA) exhibited markedly different optical and electronic properties, as manifested by an apparent red shift of the photoluminescence profiles, which was ascribed to electronic coupling between the particle-bound naphthalene groups. Electrochemical measurements exhibited consistent results where a negative shift was observed of the formal potential of the particle-bound naphthalene moieties. This was attributed to intraparticle charge delocalization that led to extended spilling of nanoparticle core electrons to the naphthalene moieties. ■ INTRODUCTIONOrganically capped metal nanoparticles have been attracting extensive interest because the material properties may be readily controlled by the chemical nature of the metal cores and the organic protecting ligands as well as their interfacial bonding interactions. 1−5 In fact, the bonding linkages at the metal−ligand interface have been observed to impact the nanoparticle dimensions, morphology, and stability; inversely, metal nanoparticles also have influence on the ligand physical and chemical property, reactivity, and configuration. 4,6,7 Of these, ruthenium nanoparticles have been intensively studied due to its stability and affinity to many organic capping ligands, such as mercapto derivatives, alkylamines, diazo, acetylene, nitrene, and carboxylate moieties. 4,7−11 For instance, for ruthenium nanoparticles functionalized by acetylene derivatives, the formation of conjugated metal−ligand π-bonds leads to intraparticle charge delocalization, and hence, the nanoparticles exhibit new optical/electronic characteristics that are analogous to those of diacetylene derivatives. 11−13 These results highlight the significance of interfacial engineering in the manipulation of nanoparticle materials properties.Conjugated metal−ligand interfacial bonds may also be produced by exploiting the unique interfacial reactivity of organic ligands on nanoparticle surfaces. For instance, we recently observed that alkene derivatives might self-assemble onto platinum nanoparticle surfaces, forming platinum−vinylidene or −acetylide bonds as a consequence of platinumcatalyzed dehydrogenation and transformation of the olefin groups. 14 In another study, 15 ruthenium nanoparticles were protected by ferrocenecarboxylates, and galvanic exchange reactions with Pd(II) led to the deposition of a s...

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Electronic conductivity of alkyne-capped ruthenium nanoparticles

Cited by 30 publications

References 37 publications

The influence of molecular mobility on the properties of networks of gold nanoparticles and organic ligands

The influence of molecular mobility on the properties of networks of gold nanoparticles and organic ligands

One-pot Synthesis of Octyne-Ruthenium on Carbon Nanoparticles

Chemical Reactivity of Naphthalenecarboxylate-Protected Ruthenium Nanoparticles: Intraparticle Charge Delocalization Derived from Interfacial Decarboxylation

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