Sky-blue emitting bridged diiridium complexes: beneficial effects of intramolecular π–π stacking

Congrave, Daniel G.; Hsu, Yu-Ting; Batsanov, Andrei S.; Beeby, Andrew; Bryce, Martin R.

Abstract

The potential of intramolecular π–π interactions to influence the photophysical properties of diiridium complexes is an unexplored topic, and provides the motivation for the present study. A series of diarylhydrazide-bridged diiridium complexes functionalised with phenylpyridine (ppy)-based cyclometalating ligands is reported. It is shown by NMR studies in solution and single crystal X-ray analysis that intramolecular π–π interactions between the bridging and cyclometalating ligands rigidify the complexes leading to high luminescence quantum efficiencies in solution and in doped films. Fluorine substituents on the phenyl rings of the bridge promote the intramolecular π–π interactions. Notably, these non-covalent interactions are harnessed in the rational design and synthesis of the first examples of highly emissive sky-blue diiridium complexes featuring conjugated bridging ligands, for which they play a vital role in the structural and photophysical properties. Experimental results are supported by computational studies.

Citation

Congrave, D. G., Hsu, Y., Batsanov, A. S., Beeby, A., & Bryce, M. R. (2018). Sky-blue emitting bridged diiridium complexes: beneficial effects of intramolecular π–π stacking. Dalton Transactions, 47(6), 2086-2098. https://doi.org/10.1039/c7dt04201a

• Journal Article Type: Article
• Acceptance Date: Dec 13, 2017
• Online Publication Date: Jan 22, 2018
• Publication Date: Feb 14, 2018
• Deposit Date: Dec 15, 2017
• Publicly Available Date: Dec 15, 2017
• Journal: Dalton Transactions
• Print ISSN: 1477-9226
• Electronic ISSN: 1477-9234
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 47
• Issue: 6
• Pages: 2086-2098
• DOI: https://doi.org/10.1039/c7dt04201a
• Public URL: https://durham-repository.worktribe.com/output/1342253