Journal
DALTON TRANSACTIONS
Volume 47, Issue 6, Pages 2086-2098Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7dt04201a
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Funding
- EPSRC [EP/L02621X/1]
- EPSRC [EP/L02621X/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [1494307, EP/L02621X/1] Funding Source: researchfish
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The potential of intramolecular pi-pi interactions to influence the photophysical properties of diiridium complexes is an unexplored topic, and provides the motivation for the present study. A series of diaryl-hydrazide-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 p-p 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 pi-pi 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.
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