(Spectro)electrochemical Properties of Anthracene Containing Triarylamine Platinum(II) Acetylides

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Abstract

The synthesis of [Pt{2}2(PPh3)2] (5) (10-ethinyl-9-di(p-anisyl)aminoanthracene=alkyne 2H) in a cis and trans configuration was achieved. Adsorption of cis-5 on AlOx as well as electrochemical oxidation led to a reductive elimination of 10,10′-(buta-1,3-diyne-1,4-diyl)bis(9-di(p-anisyl)amino-anthracene) (6). The molecular structures of the alkyne intermediate 2H, [Pt{2}Cl(PPh3)2] (4) and butadiyne 6 have been determined by single crystal X-ray diffraction. Cyclic voltammetry measurements of the platinum-acetylides trans-4, and cis- and trans-5 demonstrated, that the back donation from platinum towards the π-system results in a shift of the triarylamine and anthracene related redox processes towards lower E°′ values, when compared to the SiMe3-protected alkyne of 2 (=2SiMe3). Both platinum complex trans-5 and butadiyne 6 demonstrated that the individual arylamine and the respective anthracenyl buildings blocks can be oxidized in four one electron processes. Spectroelectrochemical studies revealed several intense intra-ligand absorptions in the NIR, demonstrating a high degree of delocalization in the ligand. However, a direct IVCT through the platinum was not observed.

Details

Original languageEnglish
Number of pages10
JournalEuropean journal of inorganic chemistry
Volume2021
Issue number25
Publication statusPublished - 7 Jul 2021
Peer-reviewedYes

External IDs

Scopus 85107990222

Keywords