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Luminescent monocyclometalated cationic gold(III) complexes: synthesis, photophysical characterization and catalytic investigations


Zehnder, Thomas N; Blacque, Olivier; Venkatesan, Koushik (2014). Luminescent monocyclometalated cationic gold(III) complexes: synthesis, photophysical characterization and catalytic investigations. Dalton Transactions, 43(31):11959-11972.

Abstract

Stable, luminescent, and cationic monocyclometalated gold(III) monoaryl complexes of the type [(ppy)Au(FMes)(L)]+[OTf]− [L = 4-phenylpyridine (3), quinoline (4), 4-fluoroaniline (5), P(OMe)3 (6), PPh3 (7)], bearing different ancillary ligands, synthesized starting from the precursor complex [(ppy)Au(FMes)(OH2)]+[OTf]− (2) are reported. The preliminary assignment of the structure of the complexes by various nuclear magnetic resonance spectroscopy techniques and elemental analysis has been further corroborated by single-crystal X-ray diffraction studies. The complexes exhibit room temperature phosphorescence in solution, in neat solids and in doped PMMA films. Detailed photophysical investigations of the complexes in solution, in neat solids and in PMMA films revealed the successful tuning of the emission quantum yield (ϕp) based on the electronic properties of the ancillary ligands. The catalytic photo-oxidation of benzylic amines to their corresponding imines using molecular oxygen as the oxidant was successfully achieved in the presence of the luminescent Au(III) complexes. It is also established that the photocatalytic performance was strongly governed by the electronic properties of the ancillary ligands on the photosensitizer as well as by the steric bulk of the substrates.

Stable, luminescent, and cationic monocyclometalated gold(III) monoaryl complexes of the type [(ppy)Au(FMes)(L)]+[OTf]− [L = 4-phenylpyridine (3), quinoline (4), 4-fluoroaniline (5), P(OMe)3 (6), PPh3 (7)], bearing different ancillary ligands, synthesized starting from the precursor complex [(ppy)Au(FMes)(OH2)]+[OTf]− (2) are reported. The preliminary assignment of the structure of the complexes by various nuclear magnetic resonance spectroscopy techniques and elemental analysis has been further corroborated by single-crystal X-ray diffraction studies. The complexes exhibit room temperature phosphorescence in solution, in neat solids and in doped PMMA films. Detailed photophysical investigations of the complexes in solution, in neat solids and in PMMA films revealed the successful tuning of the emission quantum yield (ϕp) based on the electronic properties of the ancillary ligands. The catalytic photo-oxidation of benzylic amines to their corresponding imines using molecular oxygen as the oxidant was successfully achieved in the presence of the luminescent Au(III) complexes. It is also established that the photocatalytic performance was strongly governed by the electronic properties of the ancillary ligands on the photosensitizer as well as by the steric bulk of the substrates.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:August 2014
Deposited On:20 Feb 2015 10:11
Last Modified:05 Apr 2016 18:56
Publisher:RSC Publishing
ISSN:1477-9226
Publisher DOI:https://doi.org/10.1039/c4dt01187b

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