Pyridine gold complexes. an emerging class of luminescent materials

Fernández, Eduardo J.; Laguna, Antonio; López‐de‐Luzuriaga, José M.; Monge, Miguel; Nogueras, Manuel; Olmos, M. Elena; Pérez, Javier; Rodríguez‐Castillo, María

doi:10.1007/bf03215578

Cited by 31 publications

(51 citation statements)

References 15 publications

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“…We did not observe a trend in the redshifting of absorption and emission bands with respect to the electron-accepting properties of Pys. [7] …”

Section: Photophysical Propertiesmentioning

confidence: 97%

“…This attraction provides additional stability for molecular aggregation, both in the solid and in solution, and at times leads to luminescence. [5][6][7][8] Recently, research on the Au I -and Au III -catalyzed reactions has been booming, [9][10][11] earning the phrase "gold rush." It has been proposed that the catalytic property of gold may be affected by a relativistic contraction of 6s and expansion of 5d orbitals.…”

Section: Aumentioning

confidence: 99%

“…[12] [a] Department of Chemistry, National Dong Hwa University, Hualien 97401, Taiwan [13,14] with their structural, catalytical, medicinal, liquid-crystal, and photophysical properties extensively studied. [15][16][17][18][19][20] Relatively less Au I -Py (Py = pyridine derivatives) complexes have been studied, and only recently were their properties in luminescence, [6,7] catalysis, [6,21] and solution aggregation [6] reported. [6,7,21,22] Au I complexes with both NHC and Py ligands could very likely give interesting results; however, very few such compounds have been examined.…”

Section: Aumentioning

confidence: 99%

“…[15][16][17][18][19][20] Relatively less Au I -Py (Py = pyridine derivatives) complexes have been studied, and only recently were their properties in luminescence, [6,7] catalysis, [6,21] and solution aggregation [6] reported. [6,7,21,22] Au I complexes with both NHC and Py ligands could very likely give interesting results; however, very few such compounds have been examined. [23,24] In this work, ten [Au(NHC)(Py)][PF 6 ]-type complexes are synthesized, in an attempt to gauge the influence of different 4-substituted pyridines on the structure, photophysical properties, and secondary attractive forces such as Au···Au, Au···π, and π···π interactions.…”

Section: Aumentioning

confidence: 99%

“…[2] Au I complexes possess many interesting properties, in particular, aurophilicity, [3,4] and luminescence. [5][6][7] Aurophilicity is a weak attractive force between closed-shell d 10 …”

Section: Introductionmentioning

confidence: 99%

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Gold(I) Complexes of N‐Heterocyclic Carbenes and Pyridines

et al. 2009

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Overall ten ionic [Au(NHC)(Py)][PF6]‐ and [Au2(NHC)2(Py)2][PF6]2‐type complexes [NHC = N,N′‐dialkylbenzimidazol‐2‐ylidene, denoted as R2‐bimy with alkyl (R) being methyl (Me) or ethyl (Et), and Py = 4‐substituted pyridine or 4,4′‐bipyridine] have been prepared by incorporating various Pys into the AuI‐NHC core with Au(NHC)Cl as starting material. Their crystal structures characterized by X‐ray diffraction indicate a linearly coordinated AuI center and exhibit secondary forces such as Au···Au, Au···π, or π···π interactions. The luminescent properties of these compounds were studied in the solid state. Density‐functional theory calculations on [Au(Me2‐bimy)(4‐dmapy)][PF6] [4‐dmapy = 4‐(dimethylamino)pyridine] predict the lowest electronic transition with nonzero oscillator strength is the fourth HOMO–LUMO transition. Whereas the fourth HOMO is mainly associated with the Py ligands, the LUMO is predominantly aurophilic. Four AuI‐NHC compounds were examined for their catalytic activity towards the oxidation of benzyl alcohol to aldehyde, in which the starting material [Au(Et2‐bimy)Cl] gave the highest yield. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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“…We did not observe a trend in the redshifting of absorption and emission bands with respect to the electron-accepting properties of Pys. [7] …”

Section: Photophysical Propertiesmentioning

confidence: 97%

Section: Aumentioning

confidence: 99%

Section: Aumentioning

confidence: 99%

Section: Aumentioning

confidence: 99%

“…[2] Au I complexes possess many interesting properties, in particular, aurophilicity, [3,4] and luminescence. [5][6][7] Aurophilicity is a weak attractive force between closed-shell d 10 …”

Section: Introductionmentioning

confidence: 99%

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Gold(I) Complexes of N‐Heterocyclic Carbenes and Pyridines

et al. 2009

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The Energetic Significance of Metallophilic Interactions

et al. 2019

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Metallophilic interactions are increasingly recognized as playing an important role in molecular assembly, catalysis, and bioimaging. However, present knowledge of these interactions is largely derived from solid-state structures and gas-phase computational studies rather than quantitative experimental measurements. Here, we have experimentally quantified the role of aurophilic (Au I •••Au I), platinophilic (Pt II •••Pt II), palladophilic (Pd II •••Pd II) and nickelophilic (Ni II •••Ni II) interactions in self-association and ligand-exchange processes. All of these metallophilic interactions were found to be too weak to be well-expressed in several solvents. Computational energy decomposition analyses supported the experimental finding that metallophilic interactions are overall weak, meaning that favorable dispersion and orbital hybridization contributions from M•••M binding are largely outcompeted by electrostatic or dispersion interactions involving ligand or solvent molecules. This combined experimental and computational study provides a general understanding of metallophilic interactions and indicates that great care must be taken to avoid over-attributing the energetic significance of metallophilic interactions.

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The Energetic Significance of Metallophilic Interactions

et al. 2019

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Metallophilic interactions are increasingly recognized as playing an important role in molecular assembly, catalysis, and bio‐imaging. However, present knowledge of these interactions is largely derived from solid‐state structures and gas‐phase computational studies rather than quantitative experimental measurements. Here, we have experimentally quantified the role of aurophilic (AuI⋅⋅⋅AuI), platinophilic (PtII⋅⋅⋅PtII), palladophilic (PdII⋅⋅⋅PdII), and nickelophilic (NiII⋅⋅⋅NiII) interactions in self‐association and ligand‐exchange processes. All of these metallophilic interactions were found to be too weak to be well‐expressed in several solvents. Computational energy decomposition analyses supported the experimental finding that metallophilic interactions are overall weak, meaning that favorable dispersion and orbital hybridization contributions from M⋅⋅⋅M binding are largely outcompeted by electrostatic or dispersion interactions involving ligand or solvent molecules. This combined experimental and computational study provides a general understanding of metallophilic interactions and indicates that great care must be taken to avoid over‐attributing the energetic significance of metallophilic interactions.

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Pyridine gold complexes. an emerging class of luminescent materials

Cited by 31 publications

References 15 publications

Gold(I) Complexes of N‐Heterocyclic Carbenes and Pyridines

Gold(I) Complexes of N‐Heterocyclic Carbenes and Pyridines

The Energetic Significance of Metallophilic Interactions

The Energetic Significance of Metallophilic Interactions

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