Some recent highlights in gold chemistry

Gimeno, M. Concepción; Laguna, Antonio

doi:10.1007/bf03215495

Cited by 25 publications

(24 citation statements)

References 73 publications

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“…Because the δ function is a function of position, the momentum operator, which is inherently present in the unitary transformation U (and/or Y in eq. (8) in Supporting Information), does not commute withρ e . More detail on the PCE correction of electron density can be found elsewhere.…”

Section: Picture Change Error Of Propertiesmentioning

confidence: 99%

“…They are responsible for macroscopic properties of heavy elements, such as the color and properties of gold, [1][2][3] or the liquid aggregation state of mercury, 4 they explain the high voltage of lead-acid batteries, 5 the geometries of heavy-element containing molecules 6 and the reactive behaviour of heavy elements. 7,8 The observed effects are normally attributed to a contraction of the inner shells of the heavy elements when electrons are reaching speeds close to the speed of light, which in turn influences the outer core shells and changes ionisation potentials and other physical properties. [9][10][11] The influence of relativistic effects on chemistry is therefore identifiable through shifts of spectroscopic properties with respect to non-relativistic expectations/models which are related to the energetic levels of the shell structure of atoms, 12 and also in nuclear magnetic resonance experiments.…”

Section: Introductionmentioning

confidence: 99%

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Importance of Relativistic Effects and Electron Correlation in Structure Factors and Electron Density of Diphenyl Mercury and Triphenyl Bismuth

2016

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This study investigates the possibility of detecting relativistic effects and electron correlation in single-crystal X-ray diffraction experiments using the examples of diphenyl mercury (HgPh2) and triphenyl bismuth (BiPh3). In detail, the importance of electron correlation (ECORR), relativistic effects (REL) [distinguishing between total, scalar and spin-orbit (SO) coupling relativistic effects] and picture change error (PCE) on the theoretical electron density, its topology and its Laplacian using infinite order two component (IOTC) wave functions is discussed. This is to develop an understanding of the order of magnitude and shape of these different effects as they manifest in the electron density. Subsequently, the same effects are considered for the theoretical structure factors. It becomes clear that SO and PCE are negligible, but ECORR and scalar REL are important in low- and medium-order reflections on absolute and relative scales-not in the high-order region. As a further step, Hirshfeld atom refinement (HAR) and subsequent X-ray constrained wavefunction (XCW) fitting have been performed for the compound HgPh2 with various relativistic and nonrelativistic wave functions against the experimental structure factors. IOTC calculations of theoretical structure factors and relativistic HAR as well as relativistic XCW fitting are presented for the first time, accounting for both scalar and spin-orbit relativistic effects.

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Section: Picture Change Error Of Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Importance of Relativistic Effects and Electron Correlation in Structure Factors and Electron Density of Diphenyl Mercury and Triphenyl Bismuth

2016

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“…12 Most recently, a new method of inserting gold into porphyrin complexes has been reported; this is achieved through the disproportionation of [Au(tht) 2 ]BF 4 as the source of the gold (tht = tetrahydrothiophene). 13 Further interactions between gold and porphyrins are illustrated by reports of gold nanoparticles stabilised by coating with porphyrin thioacetate derivatives. In these systems, the gold to porphyrin link occurs through appended sulfur atoms on the porphyrin periphery.…”

Section: Synthesismentioning

confidence: 99%

“…In the late 1990's, meso-tetraalkynyl porphyrins (13) were of interest because of their light-harvesting and non-linear optical properties. The lead(II) complex of 13 (R = n-Bu) was prepared by refluxing the free base porphyrin with Pb(OAc) 2 in CHCl 3 /pyridine for 1 h. This product was fully characterised by 1 H and 13 C NMR, UV-visible spectroscopy and mass spectrometry. 47 A related complex (R = Si( i Pr) 3 ) was prepared similarly using DMF as the solvent; the molecular structure exhibits discrete units of three stacked lead complexes.…”

Section: Thallium(iii) Thallium(i) In 1948 Rothemund Andmentioning

confidence: 99%

“…27 As long as the framework which delivers the intramolecular counter-anion to the trivalent metal Fig. 13 Apical view of a single-picket bismuth porphyrin (16). 56 can accommodate any steric repulsion attributed to the bismuth lone pair, then the influence of both features clearly has a stabilising effect.…”

Section: Picket Capped and Strapped Porphyrin Complexesmentioning

confidence: 99%

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Porphyrin complexes of the period 6 main group and late transition metals

2011

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Metalloporphyrin complexes of the period six metals gold, mercury, thallium, lead and bismuth are often overlooked in favour of their lighter congeners. These complexes exhibit unusual coordination geometries, prominently featuring the metal centre residing out the porphyrin plane. Not only are these compounds chemically interesting, but several applications for these complexes are beginning to emerge. Gold and bismuth porphyrins have medicinal applications including novel chemotherapeutics and sensitizers for α-radiotherapy, while gold porphyrins have applications in materials chemistry and catalysis. This perspective serves to highlight trends in the synthesis and structure of these heavy metal complexes as well as illustrate the considerations necessary for rationally designing elaborate porphyrin architectures.

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Dipodal Ferrocene‐Based Adsorbate Molecules for Self‐Assembled Monolayers on Gold

Weidner

Ballav

Zharnikov

et al. 2008

Chemistry A European J

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1,1'-Difunctionalised ferrocene derivatives have been studied, which contain groups suitable for chemisorption on gold substrates, namely -NC, -PR(2) as well as a range of sulfur-containing units like -NCS, -SR, and thienyl. Thin films on gold have been fabricated from solution with most of these adsorbate species. Film thickness, composition and structure were investigated primarily by X-ray photoelectron and near-edge X-ray absorption fine-structure spectroscopy. The quality of self-assembled monolayers fabricated from 1,1'-diisocyanoferrocene (1) and 1,1'-diisothiocyanatoferrocene (2) turned out to be superior to that of films based on the other adsorbate species investigated. In addition to the surface coordination behaviour of 1 towards gold substrates, relevant aspects of the molecular coordination chemistry of 1 have also been addressed, including the synthesis and characterisation of [(mu-1){Cr(CO)(5)}(2)], [Ag(2)(mu-1)(2)](NO(3))(2) x H(2)O and [(mu-1)(AuCl)(2)]. The crystal structure of the gold complex is governed by aurophilic interactions and can be taken as a model for the arrangement of 1 in self-assembled monolayers on gold.

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Some recent highlights in gold chemistry

Cited by 25 publications

References 73 publications

Importance of Relativistic Effects and Electron Correlation in Structure Factors and Electron Density of Diphenyl Mercury and Triphenyl Bismuth

Importance of Relativistic Effects and Electron Correlation in Structure Factors and Electron Density of Diphenyl Mercury and Triphenyl Bismuth

Porphyrin complexes of the period 6 main group and late transition metals

Dipodal Ferrocene‐Based Adsorbate Molecules for Self‐Assembled Monolayers on Gold

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