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Structural, electrochemical and photophysical behavior of Ru(ii) complexes with large bite angle sulfur-bridged terpyridyl ligands

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Abstract

Ruthenium(II) terpyridyl species typically suffer from a distortion away from the ideal octahedral geometry due to the rigidity of the terpyridine ligand. In this study we report a series of new sulfur-bridged terpyridyl ligands (1a–c) which offer enhanced flexibility due to sulfur spacers linking the pyridine rings, in addition to the ability to tune electronic properties with electron-donating (Me) and electron-withdrawing (CF3) substituents in the 4 and 4′′-positions of the sulfur-bridged ligands. The resulting Ru(II) complexes are detailed herein as both homoleptic (2a–c) and heteroleptic (3a–c) species, with the synthesis, structural characterization, photophysical and redox properties discussed, and the sulfur-bridged ligands allowing geometries closer to that of a “perfect” octahedron. All six species were found to be non-emissive at room temperature (with emissivity increasing on cooling to 77 K), and the electrochemical properties were greatly altered due to the increased bite angle of the sulfur-bridged ligands. The electrochemical and photophysical HOMO–LUMO gap can be easily tuned by altering the substituents in the 4 and 4′′-positions.

Graphical abstract: Structural, electrochemical and photophysical behavior of Ru(ii) complexes with large bite angle sulfur-bridged terpyridyl ligands

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Publication details

The article was received on 10 Aug 2019, accepted on 23 Oct 2019 and first published on 31 Oct 2019


Article type: Research Article
DOI: 10.1039/C9QI01009B
Inorg. Chem. Front., 2020, Advance Article

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    Structural, electrochemical and photophysical behavior of Ru(II) complexes with large bite angle sulfur-bridged terpyridyl ligands

    C. M. Brown, N. E. Arsenault, T. N. K. Cross, D. Hean, Z. Xu and M. O. Wolf, Inorg. Chem. Front., 2020, Advance Article , DOI: 10.1039/C9QI01009B

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