Trimethyltin-Mediated Covalent Gold–Carbon Bond Formation

Batra, Arunabh; Kladnik, Gregor; Gorjizadeh, Narjes; Meisner, Jeffrey; Steigerwald, Michael L.; Nuckolls, Colin; Quek, Su Ying; Cvetko, D.; Morgante, A.; Venkataraman, Latha

doi:10.1021/ja5061406

Cited by 25 publications

(28 citation statements)

References 28 publications

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“…Different to previous plasmon chemistries , instead here we suggest the initiation is via hot electrons, not through a redox reaction route, but through formation of [Au–C–C ● ] species near the metal surface, which induces further polymer chain growth (Scheme and SI, Scheme S2). Formation of Au–C bonds is identified in a number of previous reports , and plausible in our case, although physical attachment is also possible . We find the thickest shells around these Au NPs (Figure d) are formed from irradiating DVB monomers, which indicates a reduced chain termination rate arising when PDVB cross-links, which comes from the sterics of this polymerization that reduces the chances of two radical chain-ends meeting.…”

Section: Resultssupporting

confidence: 79%

Light-Directed Tuning of Plasmon Resonances via Plasmon-Induced Polymerization Using Hot Electrons

et al. 2017

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The precise morphology of nanoscale gaps between noble-metal nanostructures controls their resonant wavelengths. Here we show photocatalytic plasmon-induced polymerization can locally enlarge the gap size and tune the plasmon resonances. We demonstrate light-directed programmable tuning of plasmons can be self-limiting. Selective control of polymer growth around individual plasmonic nanoparticles is achieved, with simultaneous real-time monitoring of the polymerization process in situ using dark-field spectroscopy. Even without initiators present, we show light-triggered chain growth of various monomers, implying plasmon initiation of free radicals via hot-electron transfer to monomers at the Au surface. This concept not only provides a programmable way to fine-tune plasmons for many applications but also provides a window on polymer chemistry at the sub-nanoscale.

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Section: Resultssupporting

confidence: 79%

Light-Directed Tuning of Plasmon Resonances via Plasmon-Induced Polymerization Using Hot Electrons

et al. 2017

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“…The only prior mechanistic investigation of the transfer of alkyl groups from the tin atom of a stannane to gold surface that we are aware of is an ultrahigh vacuum (UHV) study of benzyltrimethylstannane interacting with Au(111) and Au(110) at low temperature. 19 Only the benzylic C–Sn bond was cleaved selectively, and this was rationalized plausibly by the stability of the benzyl relative to the methyl radical. On Au(110) but not on Au(111) the radical attached to the surface through a C–Au bond.…”

Section: Discussionmentioning

confidence: 99%

The Scope of Direct Alkylation of Gold Surface with Solutions of C₁–C₄ n-Alkylstannanes

et al. 2015

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Treatment of cleaned gold surfaces with dilute tetrahydrofuran or chloroform solutions of tetraalkylstannanes (alkyl = methyl, ethyl, n-propyl, n-butyl) or di-n-butylmethylstannyl tosylate under ambient conditions causes a self-limited growth of disordered monolayers consisting of alkyls and tin oxide. Extensive use of deuterium labeling showed that the alkyls originate from the stannane and not from ambient impurities, and that trialkylstannyl groups are absent in the monolayers, contrary to previous proposals. Methyl groups attached to the Sn atom are not transferred to the surface. Ethyl groups are transferred slowly, and propyl and butyl rapidly. In all cases, tin oxide is codeposited in submonolayer amounts. The monolayers were characterized by ellipsometry, contact angle goniometry, polarization modulated IR reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy with ferrocyanide/ferricyanide, which revealed a very low charge-transfer resistance. The thermal stability of the monolayers and their resistance to solvents are comparable with those of an n-octadecanethiol monolayer. A preliminary examination of the kinetics of monolayer deposition from a THF solution of tetra-n-butylstannane revealed an approximately half-order dependence on the bulk solution concentration of the stannane, hinting that more than one alkyl can be transferred from a single stannane molecule. A detailed structure of the attachment of the alkyl groups is not known, and it is proposed that it involves direct single or multiple bonding of one or more C atoms to one or more Au atoms.

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“…25 This reaction was subsequently observed for the model compound benzyltrimethylstannane on Au surfaces using X-ray spectroscopies to elucidate the impact of undercoordinated Au atoms on Au-C bond formation. 28 Highly conducting junctions were also demonstrated with oligophenyls with one to four phenyls (P1 -P4). The trimethylstannane was attached to the ring via an intervening methylene group to enable strong electronic overlap from the Au-C bond to the ring π-electron states.…”

Section: Electronic Conduction Characteristics Of Junctionsmentioning

confidence: 99%

Structure–Property Relationships in Atomic-Scale Junctions: Histograms and Beyond

Hybertsen

Venkataraman

2016

Acc. Chem. Res.

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Over the past 10 years, there has been tremendous progress in the measurement, modeling and understanding of structure-function relationships in single molecule junctions. Numerous research groups have addressed significant scientific questions, directed both to conductance phenomena at the single molecule level and to the fundamental chemistry that controls junction functionality. Many different functionalities have been demonstrated, including single-molecule diodes, optically and mechanically activated switches, and, significantly, physical phenomena with no classical analogues, such as those based on quantum interference effects. Experimental techniques for reliable and reproducible single molecule junction formation and characterization have led to this progress. In particular, the scanning tunneling microscope based break-junction (STM-BJ) technique has enabled rapid, sequential measurement of large numbers of nanoscale junctions allowing a statistical analysis to readily distinguish reproducible characteristics. Harnessing fundamental link chemistry has provided the necessary chemical control over junction formation, enabling measurements that revealed clear relationships between molecular structure and conductance characteristics. Such link groups (amines, methylsuflides, pyridines, etc.) maintain a stable lone pair configuration that selectively bonds to specific, undercoordinated transition metal atoms available following rupture of a metal point contact in the STM-BJ experiments. This basic chemical principle rationalizes the observation of highly reproducible conductance signatures. Subsequently, the method has been extended to probe a variety of physical phenomena ranging from basic I-V characteristics to more complex properties such as thermopower and electrochemical response. By adapting the technique to a conducting cantilever atomic force microscope (AFM-BJ), simultaneous measurement of the mechanical characteristics of nanoscale junctions as they are pulled apart has given complementary information such as the stiffness and rupture force of the molecule-metal link bond. Overall, while the BJ technique does not produce a single molecule circuit for practical applications, it has proved remarkably versatile for fundamental studies. Measured data and analysis have been combined with atomic-scale theory and calculations, typically performed for representative junction structures, to provide fundamental physical understanding of structure-function relationships. This Account integrates across an extensive series of our specific nanoscale junction studies which were carried out with the STM- and AFM-BJ techniques and supported by theoretical analysis and density functional theory based calculations, with emphasis on the physical characteristics of the measurement process and the rich data sets that emerge. Several examples illustrate the impact of measured trends based on the most probable values for key characteristics (obtained from ensembles of order 1000-10 000 individual junctions) to build a sol...

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Trimethyltin-Mediated Covalent Gold–Carbon Bond Formation

Cited by 25 publications

References 28 publications

Light-Directed Tuning of Plasmon Resonances via Plasmon-Induced Polymerization Using Hot Electrons

Light-Directed Tuning of Plasmon Resonances via Plasmon-Induced Polymerization Using Hot Electrons

The Scope of Direct Alkylation of Gold Surface with Solutions of C₁–C₄ n-Alkylstannanes

Structure–Property Relationships in Atomic-Scale Junctions: Histograms and Beyond

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Trimethyltin-Mediated Covalent Gold–Carbon Bond Formation

Cited by 25 publications

References 28 publications

Light-Directed Tuning of Plasmon Resonances via Plasmon-Induced Polymerization Using Hot Electrons

Light-Directed Tuning of Plasmon Resonances via Plasmon-Induced Polymerization Using Hot Electrons

The Scope of Direct Alkylation of Gold Surface with Solutions of C1–C4 n-Alkylstannanes

Structure–Property Relationships in Atomic-Scale Junctions: Histograms and Beyond

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The Scope of Direct Alkylation of Gold Surface with Solutions of C₁–C₄ n-Alkylstannanes