Dinuclear Lanthanide(III) complexes for light emitting surfaces and plasmonic nanomaterials

Del Giorgio, Elena (2024). Dinuclear Lanthanide(III) complexes for light emitting surfaces and plasmonic nanomaterials. University of Birmingham. Ph.D.

DelGiorgio2024PhD.pdf
Text - Accepted Version
Restricted to Repository staff only until 31 July 2025.
Available under License All rights reserved.
Download (23MB)

Abstract

Lanthanide(III) luminescence is extremely valuable for the development of optical devices. The long luminescence lifetimes, high photostability and narrow and characteristic emission peaks of lanthanides(III) are accompanied by low molar absorption coefficients, demanding sensitisation from light harvesting units via the antenna effect. In addition to careful ligand design, nanostructured plasmonic materials can enhance lanthanide(III) luminescence and overcome some of the most common limitations of luminescent materials and particularly near infrared (NIR) emission, such as poor signal to noise ratios and low quantum yields and brightness. Here, we present novel surface active bis β-diketonatelanthanide(III) complexes for the fabrication of visible and NIR emitting materials. The incorporation of thioacetate units in the ligand scaffold enables the complexes to be anchored on metallic substrates. The characteristic visible and NIR luminescence is retained upon coating on gold (Au) surfaces, and the preparation of a handheld sensing device is demonstrated as a response of the Eu(III) surfaces to F- coordination. Incorporation of the complexes to plasmonic substrates is determined to be an excellent approach for the enhancement of both visible and NIR luminescence. Plasmonic Au (pGold) surfaces, in particular, lead to exceptional resolution and intensity of NIR Nd(III) and Yb(III) emission, driving the progress of lanthanide(III) NIR light to advanced applications. Finally, the complexes are anchored on Au nanoparticles (AuNPs), producing highly emissive H2O dispersed nanomaterials. An alternative approach for the preparation of surface active bis β-diketonates is demonstrated by coordination of functionalised 1,10-phenanthroline units, also optimising the luminescent output of both the complex in solution and on AuNPs.

Type of Work:

Thesis (Doctorates > Ph.D.)

Award Type:

Doctorates > Ph.D.

Supervisor(s):