Synthesis, Redox and Spectroscopic Properties of Nindigo and a Variety of Nindigo Coordination Compounds




Nawn, Graeme

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Ligand design plays an important role in the development and control of new coordination compounds. A new ligand architecture, Nindigo, has previously been reported and this study represents an expansion of that research to gain better insights into the attributes of this multifunctional ligand family. Mono- and bis-palladium chelates of Nindigo have been synthesized with resulting electrochemical measurements allowing for the reversible redox-active nature of the ligand set to be identified. The electronic absorption properties of these complexes were also studied. The presence of the palladium centre was found to drastically perturb the ligand centered π-π* transition resulting in significant red shifts in the absorption spectra with respect to free Nindigo. The main group coordination chemistry of Nindigo was explored by generating mono- and bis-BF2 Nindigo chelates. The electrochemical and spectral properties of these compounds were investigated with both families displaying weak emission in the NIR region. The bis-BF2 chelates were found to be sensitive in nature and decompose to the mono-BF2 chelates. In addition, heteroleptic complexes of mono-BF2 Nindigo chelates with palladium were also synthesized. The redox chemistry as well as the electronic absorption characteristics of these compounds provides a conceptual bridge between the two homologues. Homoleptic zinc and copper complexes of mono-BF2 Nindigo chelates have been synthesized. The zinc derivative serves as an “innocent” system where all redox and spectral properties are ligand centered and the oxidation states of both the metal and surrounding ligands can be assigned. The copper complexes exhibit more diverse chemistry with the redox and electronic absorption properties differing dramatically from the zinc system. A combination of EPR, XPS and computational analysis suggests the copper systems to be non-innocent in nature. In addition to the bis-bidentate anionic Nindigo ligand system, the fully oxidized neutral analogue has also been synthesized. DehydroNindigo exhibits significantly different chemical behaviour from Nindigo. Bridged ruthenium dimers have been synthesized that are obtained as two isomers, cis and trans (with respect to the bridging ligand). Both isomers exhibit rich electrochemical behaviour. The mixed valence states of both species are found, electrochemically, to be extremely stable with respect to disproportionation.



Redox-active, Near Infrared, Coordination Chemistry, Nindigo, DehydroNindigo