Dinuclear RuII complexes with quinonoid bridges: tuning the electrochemical and spectroscopic properties of redox-switchable NIR dyes through judicious bridge design

Dalton Transactions : an International Journal of Inorganic Chemistry
Shubhadeep ChandraBiprajit Sarkar

Abstract

Bridging quinonoid ligands are important platforms for generating metal-based switchable optoelectronic and magnetic materials. A possible sound way of influencing the properties of the aforementioned materials is to modify the direct metal-ligand interface. We present herein a series of dinuclear RuII complexes where the set of donor atoms at the bridging quinonoid ligands range from [O,O,O,O], [O,O,O,N], [O,N,O,N] and [O,N,O,N']. Additionally, the substituents on the N-donors were varied as well (a total of eight different quinonoid bridges are compared). We also present a mononuclear RuII complex for comparison purposes. The dinuclear complexes act as switchable NIR dyes, absorbing in the NIR region in their mixed-valent RuII/RuIII form but not in the neighboring RuII/RuII and RuIII/RuIII states. The switching potentials (the potentials at which NIR absorptions appear) and the λmax of the NIR band can be fine-tuned by varying the donor atoms as well as the electron-donating ability of the substituents on the nitrogen atoms (tuning E by ca. 0.4 V and λmax by ca. 450 nm). Introducing more electron-rich substituents at the nitrogen atoms of the bridge results in higher band energies and more cathodic redox potentials. Unsymmetr...Continue Reading

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Citations

May 18, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Dai OyamaTsugiko Takase
Jan 26, 2022·Dalton Transactions : an International Journal of Inorganic Chemistry·Sanjib PandaGoutam Kumar Lahiri

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Methods Mentioned

BETA
X-ray
column chromatography
NMR

Software Mentioned

SHELXT
PLATON
Molekel
ORCA
Saint
SHELXL
SADABS
APEX3

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