Soft-landing Isolation of Gas-phase-synthesized Transition Metal−Benzene Complexes into a Fluorinated Self-assembled Monolayer Matrix

Nagaoka, Shuhei; Ikemoto, Kaori; Matsumoto, Takeshi; Mitsui, Masaaki; Nakajima, Atsushi

doi:10.1021/jp8055784

Cited by 19 publications

(37 citation statements)

References 68 publications

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“…Deposition of polyatomic ions onto surfaces with retention of charge was reported by the same group 20 years later . Subsequent studies have shown that complex ions including peptides, − proteins, − organometallic complexes, − and metal clusters ,− may be soft landed onto substrates intact. For example, previous studies from our laboratory examined the charge reduction and neutralization of protonated peptides ions ,− ,− as well as cationic metal–salen , and ruthenium tris(bipyridine) , organometallic complexes soft landed onto different SAMs.…”

Section: Introductionmentioning

confidence: 89%

Coverage-Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-Selected Ions

2012

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The ionic charge state of monodisperse multiply charged cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution and introduced into the gas phase by electrospray ionization. Mass selection was employed to isolate a multiply charged cationic cluster species (Au 11 L 5 3+ , m/z = 1409, L = 1,3-bis(diphenylphosphino)-propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at controlled coverages of 10 11 and 10 12 clusters. Employing the spatial profiling capabilities of in situ time-of-flight secondary ion mass spectrometry (TOF-SIMS), it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano 2012, 6, 573), the coverage of cationic gold clusters on the surface may be used to control the relative abundance of different charge states of the soft landed multiply charged clusters. In the case of a 1H,1H,2H,2H-perfluorodecanethiol monolayer (FSAM) almost complete retention of charge by the deposited Au 11 L 5 3+ clusters was observed at a lower coverage of 10 11 clusters. In contrast, at a higher coverage of 10 12 clusters, pronounced reduction of charge to Au 11 L 5 2+ and Au 11 L 5 + was observed on the FSAM. When soft landed onto 16-and 11-mercaptohexadecanoic acid surfaces on gold (16,11-COOH-SAMs), the mass-selected Au 11 L 5 3+ clusters exhibited partial reduction of charge to Au 11 L 5 2+ at lower coverage and additional reduction of charge to both Au 11 L 5 2+ and Au 11 L 5 + at higher coverage. On the surface of the 1-dodecanethiol (HSAM) monolayer, the most abundant charge state was found to be Au 11 L 5 2+ at lower coverage and Au 11 L 5 + at higher coverage, respectively. A coverage-dependent electron tunneling mechanism is proposed to account for the observed reduction of charge of mass-selected multiply charged gold clusters soft landed on SAMs. The results demonstrate that one of the critical parameters that influence the chemical and physical properties of supported metal clusters, ionic charge state, may be controlled by selecting the coverage of charged species soft landed onto surfaces. ■ INTRODUCTIONThe highly size-dependent physical and chemical properties 1−5 of small metal clusters have made them the focus of considerable research attention in the chemistry and materials science communities. The eventual goal of much of this research is to develop economical techniques for the scalable synthesis of metal clusters of an exact size and composition. Such precise methods will enable the rational assembly of cluster-based materials 6,7 with desired attributes from welldefined metal particles having distinctive optical, 8−10 electronic, 11−13 or catalytic properties. 14,15 Indeed, metal nanoparticles have already shown considerable promise for applications in photothermal therapeutic treatments, 16 as contrast agents in biological and cellular imaging, ...

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Section: Introductionmentioning

confidence: 89%

Coverage-Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-Selected Ions

2012

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“…This intact deposition of projectile ions impinging on surfaces at low collision energies (<100 eV) was referred to as soft-landing, and this process may occur with or without retention of the initial ion charge [2][3][4]. Experiments of soft-landing have involved a wide variety of projectile ions, including small and medium-size polyatomic ions [1,[5][6][7][8][9][10][11][12], clusters [13][14][15][16][17][18][19][20][21][22][23][24], peptides [11,23,[25][26][27][28][29][30], proteins [25,31,32], a nucleotide [33], and intact viruses [34,35]. SAMs were used in many of these experiments because their well-characterized structure, controllable surface properties and biocompatibility make them convenient targets for biological and medical applications [36].…”

Section: Introductionmentioning

confidence: 99%

Intermolecular potentials for simulations of collisions of SiNCS+ and (CH3)2SiNCS+ ions with fluorinated self-assembled monolayers

et al. 2012

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Analytical potential energy functions were developed for interactions of SiNCS + and (CH 3) 2 SiNCS + ions with perfluorinated self-assembled monolayer (F-SAM) surfaces. Two model compounds were used to represent an F-SAM: CF 4 and nine chains of perfluorobutane forming a miniSAM structure. Density functional theory plus dispersion (DFT-D) calculations were carried out to compute intermolecular potential energy curves (IPECs) for these systems. The applied DFT-D method (specifically, B97-D) was successfully tested against high-level wavefunction calculations performed on the smallest system investigated. The IPECs calculated at the B97-D level were fitted to analytical potentials of the Buckingham type. The calculations show that the parameters obtained from the fits involving CF 4 are transferable to the miniSAM system, provided the fittings are conducted with caution, thus corroborating that CF 4 is a good model for parameterizing intermolecular potentials for interactions of gases with F-SAM surfaces.

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“…The intensities of IR peaks are almost the same as that on Au 25 :SC12 on a bare Au(111) substrate, although the transfer substrate is changed to a hydrophobic nature of F-SAM, on Au(111). Indeed, water contact angles of Au(111) and F-SAM are 0 and ∼112°, respectively. However, the result shows that the transfer ratio of the number of Au 25 :SC12 is not improved by the F-SAM.…”

Section: Resultsmentioning

confidence: 99%

Vibrational Spectra of Thiolate-Protected Gold Nanocluster with Infrared Reflection Absorption Spectroscopy: Size- and Temperature-Dependent Ordering Behavior of Organic Monolayer

et al. 2019

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Vibrational spectra of thiolate-protected gold nanoclusters, prepared in a monolayer manner using the Langmuir–Blodgett method, were measured by means of infrared reflection absorption spectroscopy (IRAS). A transferred monolayer of gold nanoclusters ligated by dodecanethiolate or 2-phenylethane-1-thiolate onto a single-crystal gold (Au) surface of Au(111) exhibits worthy IRAS spectra that reveal temperature-dependent behaviors from 100 to 340 K as well as comprehensive peak assignments based on density functional theory calculations: the conformation change in ligands between all trans and gauche defect forms with temperature. In addition to the temperature dependence, the cluster size dependence of alkyl and phenyl moieties is discussed, compared with the IRAS spectra of the corresponding self-assembled monolayers (SAMs) on Au(111). Ligands spreading three-dimensionally from the Au core determine the coordination structure of the ligated Au nanoclusters.

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Soft-landing Isolation of Gas-phase-synthesized Transition Metal−Benzene Complexes into a Fluorinated Self-assembled Monolayer Matrix

Cited by 19 publications

References 68 publications

Coverage-Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-Selected Ions

Coverage-Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-Selected Ions

Intermolecular potentials for simulations of collisions of SiNCS+ and (CH3)2SiNCS+ ions with fluorinated self-assembled monolayers

Vibrational Spectra of Thiolate-Protected Gold Nanocluster with Infrared Reflection Absorption Spectroscopy: Size- and Temperature-Dependent Ordering Behavior of Organic Monolayer

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