Influence of heavy atom effect on the photophysics of coinage metal carbene-metal-amide emitters

Feng, Jiale, Reponen, Antti‐Pekka M., Romanov, Alexander S., Linnolahti, Mikko, Bochmann, Manfred, Greenham, Neil C., Penfold, Thomas and Credgington, Dan (2020) Influence of heavy atom effect on the photophysics of coinage metal carbene-metal-amide emitters. Advanced Functional Materials. ISSN 1616-301X

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Abstract

The effect of the heavy metal atom on the photophysics of carbene-metal-amide (CMA) photoemitters is explored, where the metal bridge is either Au, Ag, or Cu. Spectroscopic investigations reveal the coupling mechanism responsible for communication between the singlet and triplet manifolds. The photophysical properties do not reflect expected trends based upon the heavy atom effect, as both direct coupling between charge-transfer states and spin-vibronic coupling via a ligand-centered triplet state are present. Direct coupling is weakest for CMA(Ag), increasing the importance of the spin-vibronic pathway and rendering its properties more sensitive to inter-state energy gaps than for the Au and Cu-bridged analogues. The measured activation energy correlates with the expected exchange energy of the charge-transfer state, which is also closely related to the length of the bonds joining the carbene and amide ligands, and decreases in the order CMA(Cu) > CMA(Au) > CMA(Ag). These findings reveal that reducing interference between charge-transfer and ligand-centers excited, and minimizing exchange energy, are required for developing efficient luminescent CMA complexes.

Item Type: Article
Uncontrolled Keywords: carbene-metal-amide,charge-transfer,heavy atom effect,intersystem crossing,photoluminescence,photophysics,chemistry(all),materials science(all),condensed matter physics ,/dk/atira/pure/subjectarea/asjc/1600
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: LivePure Connector
Date Deposited: 28 Sep 2020 23:59
Last Modified: 20 Oct 2020 23:56
URI: https://ueaeprints.uea.ac.uk/id/eprint/77018
DOI: 10.1002/adfm.202005438

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