- Axial and Azimuthal Angle Determination with Surface-Enhanced Raman Spectroscopy: Thiophenol on Copper, Silver, and Gold Metal Surfaces
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Raman spectra of noble-metal phenylthiolates and the corresponding surface-enhanced Raman (SER) spectra of the surface species on copper, silver, and gold are reported.Periodic trends were found in both the bulk Raman spectra of the phenylthiolates and the SER spectra.Intensities of the Raman spectra approach that of liquid thiophenol as the metal changes from copper to silver to gold.The SER spectra were used to obtain orientations of the thiophenol species at the noble-metal surfaces.Orientations were determined through the electric field enhancement of vibrations normal to the metal surface.The model developed in this paper allows one to determine both the azimuthal and axial angles of C2ν molecules at surfaces.This is possible by performing the SERS measurement in media of differing indexes of refraction.For silver and gold we found the axial angle Θ = 85 and 76 deg, respectively.The azimuthal angle Φ was found to vary from 32 to 0 deg from silver to gold.The SER spectra of copper were too weak for accurate angle determinations with a surrounding media other than air.However, the SER spectrum observed on copper in air does indicate a near-perpendicular orientation.
- Carron, Keith T.,Hurley, L. Gayle
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- Post-synthetic functionalization and ligand exchange reactions in gold(i) phenylthiolate-based coordination polymers
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Gold thiolate coordination polymers (CPs) are anisotropic materials with 1D or 2D networks exhibiting a large palette of photoluminescence properties. In this paper, we show that, from both lamellar acid and ester, [Au(p-SPhCO2X)]n CPs (X = H, Me), it is possible to perform post-synthesis esterification or saponification reactions. Three new 2D phases with X = Na, K and Cs were isolated. In addition, ligand exchange reactions were carried out from 1D [Au(p-SPh)]n CP and 2D [Au(p-SPhCO2X)]n CPs (X = H, Me) and the transformations from 1D to 2D structures and vice versa point out a mechanism of dissolution and recrystallization that is governed by the nature of the ligands and the presence of weak interactions. The obtained compounds exhibit solid state and RT photoemission characteristic of their structure. This journal is
- Okhrimenko, Larysa,Cibaka Ndaya, Cynthia,Fateeva, Alexandra,Ledoux, Gilles,Demessence, Aude
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p. 17970 - 17975
(2020/11/02)
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- A complex of gold(I) benzenethiolate with isocyanide: Synthesis and crystal and molecular structures
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2,6-Dimethylphenyl isocyanide forms complexes with gold(I) chloride (complex 4) and gold(I) benzenethiolate (complex 5) but forms no stable complexes with gold alkanethiolates. A reaction of complex 5 with tetramethylthiuram disulfide yields gold(I) dimethyldithiocarbamate. Stable gold(III) derivatives cannot be obtained in such a way. Shortened intermolecular Au...Au contacts in complexes 4 and 5 (X-ray diffraction) suggest the presence of "aurophilic" interactions in them.
- Dyadchenko,Belov,Dyadchenko,Slovokhotov,Banaru,Lemenovskii
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p. 539 - 543
(2011/02/16)
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- Synthesis, crystal and molecular structure of gold(I) thiophenolate with 4′-ferrocenyl[1,1′]biphenylisocyanides
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The syntheses of ferrocenylbiphenylisocyanide gold(I) thiophenolato complexes are described. The preparative route starts from ferrocenylphenylbromide and proceeds in six steps to yield the desired gold(I) complexes, (thiophenolato)gold{(4′-ferrocenyl[1,1′]biphenyl-4-yl)isocya nide} (11) and (thiophenolato)gold{(4′-ferrocenyl-3,5-dimethyl[1,1′]bipheny l-4-yl)isocyanide} (12) in good yields. The synthetic pathways were developed as a first step toward realizing the goal of preparing metallomesogens based on ferrocenyl-polyphenylenes coordinated to gold(I) thiophenolates, in which long chain alkoxy groups are substituted para to sulfur on the phenyl ring. The crystal structures of (chloro)gold{(4′-ferrocenyl[1,1′]biphenyl-4-yl)is ocyanide} (9) and 12 are reported. Complex 9 crystallizes in the space group P21/c and 12 crystallizes in P21/n. Complexes 9 and 12 show short intermolecular Au-Au contacts of 3.3765(7) ? and 3.3334(3) ?, respectively.
- Dyadchenko,Belov,Lemenovskii,Antipin,Lyssenko,Bruce,Bruce
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p. 304 - 309
(2010/03/30)
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- Construction of luminescent gold(I) aryl thiolates via isonitrilegold(I) complexes: Influence of synthetic methodology and the thiolate ligand on structure and properties
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Gold Thiolate Polymers ([ArSAu]n) were prepared via two synthetic routes - the direct reaction of an aromatic thiolate (ArSH) with HAuCl4, or the reaction of an isonitrilegold(I) chloride complex with a thiolate anion. The former rou
- Bachman, Robert E.,Bodolosky-Bettis, Sheri A.
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p. 1491 - 1499
(2010/06/15)
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- Coordination of pyridinethiols in gold(I) complexes
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High-yield synthesis of gold(I) thionato complexes, bis(pyridine-2- thionato)gold(I) chloride (1) and bis(pyridine-4-thionato)gold(I) chloride (2), are described. According to their solid-state structures, a linear coordination of Au(I), equiplanar coordination of the ligands and two weak γ-agostic interactions are found in both of these complexes despite of different relative positions of N and S atoms in the pyridinethionato ligands. Density functional theory calculations on 1 and 2 reproduce the observed X-ray structures. Even though the C-H...Au interactions of Au(I) and two pyridine moieties (2.83 and 2.88 A in 1 and 2.86 A in 2) are relatively weak, according to calculations they seem to provide further stabilization for the coordination and orientation of the ligands. In 1 the shortest Au...Au distances of 3.50 A indicate that aurophilic interactions, even though weak, are present in the solid state, whereas in 2 these interactions are absent.
- Raeisaenen, Minna T.,Runeberg, Nino,Klinga, Martti,Nieger, Martin,Bolte, Michael,Pyykkoe, Pekka,Leskelae, Markku,Repo, Timo
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p. 9954 - 9960
(2008/10/09)
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- The direct electrochemical synthesis of thiolato complexes of copper, silver, and gold; the molecular structure of 2*CH3CN
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The electrochemical oxidation of anodic copper or silver (= M) into non-aqueous solutions of RSH (R = alkyl, axyl) gives MISR as insoluble materials in high yield.In the presence of 1,10-phenanthroline (= L), the products are MISR*phen for M = Cu, but not Ag.Gold resists oxidation under such conditions, and AuISR (R = n-C4H9, C6H5) was obtained in only poor yield.The crystal structure of the solvated dimeric adduct 2*CH3CN is triclinic, with a = 10.682(3) Angstroem, b = 11.729(4) Angstroem, c = 15.608(5) Angstroem, α = 76.87(2) deg, β = 76.35(2) deg, γ = 68.07(2) deg, V = 1742(1) Angstroem3, Z = 2 and space group P1.The structure is based on a folded Cu2S2 ring with an unusually short Cu-Cu distance of 2.613(3) Angstroem.Each copper atom has CuS2N2 pseudo-tetrahedral stereochemistry, with Cu-S = 2.337 Angstroem (av) and Cu-N = 2.10 Angstroem (av).
- Chadha, Raj K.,Kumar, Rajesh,Tuck, Dennis G.
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p. 1336 - 1342
(2007/10/02)
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- Synthesys and Low-frequency Vibrational Spectra of Some Bis(alkanethiolato)- and Bis(benzenethiolato)-aurate(I) Complexes
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Salts containing bis (alkanethiolato)aurate(I) ions, - R=Me or t-Bu), or bis(benzenethiolato)aurate(I) ions, -, have been prepared from the corresponding dihalogenoaurate(I) salts by displacement of halide by thiol
- Bowmaker, Graham A.,Dobson, Brian C.
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p. 267 - 270
(2007/10/02)
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- Interaction of thiosilanes and disilthianes with some transitional and post-transitional metal halides
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Thiosilanes and disilthianes do not form stable co-ordination complexes with transitional and post-transitional metal halides, but invariably undergo fission of the silicon-sulphur bonds to give alkyl/arylmercaptides, sulphides or sulphonium derivatives o
- Abel,Jenkins
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p. 285 - 289
(2007/10/18)
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