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Gold Coordination Chemistry and Applications
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Gold Coordination Chemistry and Applications

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Applied Chemistry".

Deadline for manuscript submissions: closed (15 November 2021) | Viewed by 18305

Special Issue Editors

Dr. Marco Baron

E-Mail Website
Guest Editor
Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy
Interests: gold complexes; N-heterocylic carbenes; homogeneous catalysis; luminescence; aurophilicity
Prof. Dr. Cristina Tubaro

E-Mail Website
Guest Editor
Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy
Interests: N-heterocyclic carbene ligands; late transition metal complexes; coordination and organometallic chemistry; homogeneous catalysis; gold complexes
Prof. Dr. Andrea Biffis

E-Mail Website
Guest Editor
Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy
Interests: late transition metal catalysts; metal nanoclusters; cooperative catalysis; biphasic catalysis

Special Issue Information

Dear Colleagues,

During the last two decades, gold complexes have developed into an important class of new compounds which are engaged in biomedical and catalytic applications and in many other areas, thus attracting ever-growing attention from the scientific community.

This Special Issue is aimed at highlighting the most recent advances on gold coordination chemistry, as well as on the application of gold complexes. Therefore, for this Special Issue, we welcome contributions related to all aspects of this topic, covering novel synthesis, reactivity, advanced applications (for example, in catalysis, bioinorganic chemistry, material science), as well as mechanistic or thoretical studies, showcasing the variety and versatility of gold compounds achieved to date.

A fascinating aspect of gold coordination chemistry is that it is rapidly and continuously developing. In this regard, special attention will be given to the most recent and innovative aspects of gold coordination chemistry. In fact, in addition to papers dealing with traditional molecular complexes, particularly encouraged is the submission of contributions dealing with nonconventional interaction modes of gold centres (aurophilic interaction, hydrogen bonds, etc.), with ligand stabilized multinuclear gold compounds/gold nanoclusters, with supramolecular architechtures based on gold, and of course with the properties and potential applications of the resulting adducts. Thus, this Special Issue will also serve as a way of opening up new opportunities for sharing knowledge and promoting collaborations between researchers dealing with the different facets of this complex field today.

Short review articles, full papers, and communications are all welcome.

Dr. Marco Baron
Prof. Cristina Tubaro
Prof. Dr. Andrea Biffis
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Gold complexes
  • Organometallic chemistry
  • Ligand design
  • Homogeneous catalysis
  • Bioinorganic chemistry
  • Photophysics
  • Supramolecular chemistry
  • Gold nanoclusters

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Published Papers (7 papers)

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Research

9 pages, 2539 KiB  
Article
Dinuclear gold(I) Complexes with Bidentate NHC Ligands as Precursors for Alkynyl Complexes via Mechanochemistry
by Valentina Stoppa, Edoardo Battistel, Marco Baron, Paolo Sgarbossa, Andrea Biffis, Gregorio Bottaro, Lidia Armelao and Cristina Tubaro
Molecules 2022, 27(13), 4317; https://doi.org/10.3390/molecules27134317 - 5 Jul 2022
Cited by 3 | Viewed by 2014
Abstract
The use of alkynyl gold(I) complexes covers different research fields, such as bioinorganic chemistry, catalysis, and material science, considering the luminescent properties of the complexes. Regarding this last application, we report here the synthesis of three novel dinuclear gold(I) complexes of the general [...] Read more.
The use of alkynyl gold(I) complexes covers different research fields, such as bioinorganic chemistry, catalysis, and material science, considering the luminescent properties of the complexes. Regarding this last application, we report here the synthesis of three novel dinuclear gold(I) complexes of the general formula [(diNHC)(Au-C≡CPh)2]: two Au-C≡CPh units are connected by a bridging di(N-heterocyclic carbene) ligand, which should favor the establishment of semi-supported aurophilic interactions. The complexes can be easily synthesized through mechanochemistry upon reacting the pristine dibromido complexes [(diNHC)(AuBr)2] with phenylacetylene and KOH. Interestingly, we were also able to isolate the monosubstituted complex [(diNHC)(Au-C≡CPh)(AuBr)]. The gold(I) species were fully characterized by multinuclear NMR spectroscopy and mass spectrometry. The emission properties were also evaluated, and the salient data are comparable to those of analogous compounds reported in the literature. Full article
(This article belongs to the Special Issue Gold Coordination Chemistry and Applications)
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12 pages, 3329 KiB  
Article
Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3
by Shengyang Guan, David C. Mayer, Christian Jandl, Sebastian J. Weishäupl, Angela Casini and Alexander Pöthig
Molecules 2021, 26(15), 4404; https://doi.org/10.3390/molecules26154404 - 22 Jul 2021
Viewed by 2775
Abstract
A new solvatomorph of [Au3(1-Methylimidazolate)3] (Au3(MeIm)3)—the simplest congener of imidazolate-based Au(I) cyclic trinuclear complexes (CTCs)—has been identified and structurally characterized. Single-crystal X-ray diffraction revealed a dichloromethane solvate exhibiting remarkably short intermolecular Au⋯Au distances (3.2190(7) Å). [...] Read more.
A new solvatomorph of [Au3(1-Methylimidazolate)3] (Au3(MeIm)3)—the simplest congener of imidazolate-based Au(I) cyclic trinuclear complexes (CTCs)—has been identified and structurally characterized. Single-crystal X-ray diffraction revealed a dichloromethane solvate exhibiting remarkably short intermolecular Au⋯Au distances (3.2190(7) Å). This goes along with a dimer formation in the solid state, which is not observed in a previously reported solvent-free crystal structure. Hirshfeld analysis, in combination with density functional theory (DFT) calculations, indicates that the dimerization is generally driven by attractive aurophilic interactions, which are commonly associated with the luminescence properties of CTCs. Since Au3(MeIm)3 has previously been reported to be emissive in the solid-state, we conducted a thorough photophysical study combined with phase analysis by means of powder X-ray diffraction (PXRD), to correctly attribute the photophysically active phase of the bulk material. Interestingly, all investigated powder samples accessed via different preparation methods can be assigned to the pristine solvent-free crystal structure, showing no aurophilic interactions. Finally, the observed strong thermochromism of the solid-state material was investigated by means of variable-temperature PXRD, ruling out a significant phase transition being responsible for the drastic change of the emission properties (hypsochromic shift from 710 nm to 510 nm) when lowering the temperature down to 77 K. Full article
(This article belongs to the Special Issue Gold Coordination Chemistry and Applications)
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10 pages, 2969 KiB  
Article
Argon Adsorption on Cationic Gold Clusters Aun+ (n ≤ 20)
by Piero Ferrari and Ewald Janssens
Molecules 2021, 26(13), 4082; https://doi.org/10.3390/molecules26134082 - 4 Jul 2021
Cited by 6 | Viewed by 2573
Abstract
The interaction of Aun+ (n ≤ 20) clusters with Ar is investigated by combining mass spectrometric experiments and density functional theory calculations. We show that the inert Ar atom forms relatively strong bonds with Aun+. The strength [...] Read more.
The interaction of Aun+ (n ≤ 20) clusters with Ar is investigated by combining mass spectrometric experiments and density functional theory calculations. We show that the inert Ar atom forms relatively strong bonds with Aun+. The strength of the bond strongly varies with the cluster size and is governed by a fine interplay between geometry and electronic structure. The chemical bond between Aun+ and Ar involves electron transfer from Ar to Au, and a stronger interaction is found when the Au adsorption site has a higher positive partial charge, which depends on the cluster geometry. Au15+ is a peculiar cluster size, which stands out for its much stronger interaction with Ar than its neighbors, signaled by a higher abundance in mass spectra and a larger Ar adsorption energy. This is shown to be a consequence of a low-coordinated Au adsorption site in Au15+, which possesses a large positive partial charge. Full article
(This article belongs to the Special Issue Gold Coordination Chemistry and Applications)
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15 pages, 2681 KiB  
Article
Cytotoxicity Induction by the Oxidative Reactivity of Nanoparticles Revealed by a Combinatorial GNP Library with Diverse Redox Properties
by Shenqing Wang, Xiliang Yan, Gaoxing Su and Bing Yan
Molecules 2021, 26(12), 3630; https://doi.org/10.3390/molecules26123630 - 14 Jun 2021
Cited by 3 | Viewed by 2245
Abstract
It is crucial to establish relationship between nanoparticle structures (or properties) and nanotoxicity. Previous investigations have shown that a nanoparticle’s size, shape, surface and core materials all impact its toxicity. However, the relationship between the redox property of nanoparticles and their toxicity has [...] Read more.
It is crucial to establish relationship between nanoparticle structures (or properties) and nanotoxicity. Previous investigations have shown that a nanoparticle’s size, shape, surface and core materials all impact its toxicity. However, the relationship between the redox property of nanoparticles and their toxicity has not been established when all other nanoparticle properties are identical. Here, by synthesizing an 80-membered combinatorial gold nanoparticle (GNP) library with diverse redox properties, we systematically explored this causal relationship. The compelling results revealed that the oxidative reactivity of GNPs, rather than their other physicochemical properties, directly caused cytotoxicity via induction of cellular oxidative stress. Our results show that the redox diversity of nanoparticles is regulated by GNPs modified with redox reactive ligands. Full article
(This article belongs to the Special Issue Gold Coordination Chemistry and Applications)
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15 pages, 3091 KiB  
Article
Complexes with Atomic Gold Ions: Efficient Bis-Ligand Formation
by Felix Duensing, Elisabeth Gruber, Paul Martini, Marcelo Goulart, Michael Gatchell, Bilal Rasul, Olof Echt, Fabio Zappa, Masoomeh Mahmoodi-Darian and Paul Scheier
Molecules 2021, 26(12), 3484; https://doi.org/10.3390/molecules26123484 - 8 Jun 2021
Cited by 3 | Viewed by 2317
Abstract
Complexes of atomic gold with a variety of ligands have been formed by passing helium nanodroplets (HNDs) through two pickup cells containing gold vapor and the vapor of another dopant, namely a rare gas, a diatomic molecule (H2, N2, [...] Read more.
Complexes of atomic gold with a variety of ligands have been formed by passing helium nanodroplets (HNDs) through two pickup cells containing gold vapor and the vapor of another dopant, namely a rare gas, a diatomic molecule (H2, N2, O2, I2, P2), or various polyatomic molecules (H2O, CO2, SF6, C6H6, adamantane, imidazole, dicyclopentadiene, and fullerene). The doped HNDs were irradiated by electrons; ensuing cations were identified in a high-resolution mass spectrometer. Anions were detected for benzene, dicyclopentadiene, and fullerene. For most ligands L, the abundance distribution of AuLn+ versus size n displays a remarkable enhancement at n = 2. The propensity towards bis-ligand formation is attributed to the formation of covalent bonds in Au+L2 which adopt a dumbbell structure, L-Au+-L, as previously found for L = Xe and C60. Another interesting observation is the effect of gold on the degree of ionization-induced intramolecular fragmentation. For most systems gold enhances the fragmentation, i.e., intramolecular fragmentation in AuLn+ is larger than in pure Ln+. Hydrogen, on the other hand, behaves differently, as intramolecular fragmentation in Au(H2)n+ is weaker than in pure (H2)n+ by an order of magnitude. Full article
(This article belongs to the Special Issue Gold Coordination Chemistry and Applications)
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13 pages, 1581 KiB  
Article
Monitoring of the Pre-Equilibrium Step in the Alkyne Hydration Reaction Catalyzed by Au(III) Complexes: A Computational Study Based on Experimental Evidences
by Flavio Sabatelli, Jacopo Segato, Leonardo Belpassi, Alessandro Del Zotto, Daniele Zuccaccia and Paola Belanzoni
Molecules 2021, 26(9), 2445; https://doi.org/10.3390/molecules26092445 - 22 Apr 2021
Cited by 5 | Viewed by 2329
Abstract
The coordination ability of the [(ppy)Au(IPr)]2+ fragment [ppy = 2-phenylpyridine, IPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene] towards different anionic and neutral X ligands (X = Cl−, BF4−, OTf−, H2O, 2-butyne, 3-hexyne) commonly involved in [...] Read more.
The coordination ability of the [(ppy)Au(IPr)]2+ fragment [ppy = 2-phenylpyridine, IPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene] towards different anionic and neutral X ligands (X = Cl−, BF4−, OTf−, H2O, 2-butyne, 3-hexyne) commonly involved in the crucial pre-equilibrium step of the alkyne hydration reaction is computationally investigated to shed light on unexpected experimental observations on its catalytic activity. Experiment reveals that BF4− and OTf− have very similar coordination ability towards [(ppy)Au(IPr)]2+ and slightly less than water, whereas the alkyne complex could not be observed in solution at least at the NMR sensitivity. Due to the steric hindrance/dispersion interaction balance between X and IPr, the [(ppy)Au(IPr)]2+ fragment is computationally found to be much less selective than a model [(ppy)Au(NHC)]2+ (NHC = 1,3-dimethylimidazol-2-ylidene) fragment towards the different ligands, in particular OTf− and BF4−, in agreement with experiment. Effect of the ancillary ligand substitution demonstrates that the coordination ability of Au(III) is quantitatively strongly affected by the nature of the ligands (even more than the net charge of the complex) and that all the investigated gold fragments coordinate to alkynes more strongly than H2O. Remarkably, a stabilization of the water-coordinating species with respect to the alkyne-coordinating one can only be achieved within a microsolvation model, which reconciles theory with experiment. All the results reported here suggest that both the Au(III) fragment coordination ability and its proper computational modelling in the experimental conditions are fundamental issues for the design of efficient catalysts. Full article
(This article belongs to the Special Issue Gold Coordination Chemistry and Applications)
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13 pages, 8365 KiB  
Article
Evaluation of the Antioxidant Capacities of Antarctic Macroalgae and Their Use for Nanoparticles Production
by N. González-Ballesteros, M. C. Rodríguez-Argüelles and M. Lastra-Valdor
Molecules 2021, 26(4), 1182; https://doi.org/10.3390/molecules26041182 - 23 Feb 2021
Cited by 12 | Viewed by 2615
Abstract
Macroalgae are sources of bioactive compounds that are interesting from both a chemical and a medical point of view. Although their use in biomedicine has increased significantly in recent years, tests conducted to date have been mostly related to species from temperate latitudes, [...] Read more.
Macroalgae are sources of bioactive compounds that are interesting from both a chemical and a medical point of view. Although their use in biomedicine has increased significantly in recent years, tests conducted to date have been mostly related to species from temperate latitudes, with the potential application of Antarctic biodiversity being minor. The wide variety of algae species present on Antarctic coastal areas can be a source of new antioxidants. Bearing this in mind, the brown macroalgae Desmarestia antarctica (DA) and the red Iridaea cordata (IC) were selected for the preparation of aqueous extracts with the aim of analyzing their antioxidant activity. This analysis was performed by determining reducing power, total phenolic content, and 2,2-diphenyl-1-picrylhydrazyl free radical scavenging activity. Furthermore, both extracts were employed to synthesize gold and silver nanoparticles. The nanomaterials were fully characterized by means of UV-Visible spectroscopy, transmission electron microscopy, Z potential measurements, and Fourier transform infrared spectroscopy, which confirmed the formation of stable, spherical nanoparticles with mean diameters of 13.7 ± 3.1 and 17.5 ± 3.7 nm for Ag@DA and Ag@IC and 12.6 ± 1.9 and 12.3 ± 1.6 nm for Au@DA and Au@IC. Antioxidant assays were performed after the synthesis of the nanomaterials to evaluate their possible synergistic effect with the extracts. The results suggest that polysaccharides and proteins may play a key role in the process of reduction and stabilization. Finally, for the sake of comparison, the results obtained for the Antarctic macroalgae Desmarestia menziesii and Palmaria decipiens have also been considered in the present work. Full article
(This article belongs to the Special Issue Gold Coordination Chemistry and Applications)
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