Photo–Click Chemistry to Design Highly Efficient Lanthanide β‑Diketonate Complexes Stable under UV Irradiation

• Published in: Chemistry of materials 2013-02, Vol.25 (4), p.586-598
• Main Authors: Lima, Patrícia P, Nolasco, Mariela M, Paz, Filipe A. A, Ferreira, Rute A. S, Longo, Ricardo L, Malta, Oscar L, Carlos, Luís D
• Format: Article
• Language: English
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/cm303776x

Europium ( t -Eu) and gadolinium ( t -Gd) β-diketonate complexes with photoactive t-bpete ligand, [Ln(btfa)3(t-bpete)(MeOH)] (Ln = Eu, Gd), where btfa– and t-bpete are 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and trans-1,2-bis(4-pyridyl)ethylene, respectively, were synthesized, characterized by vibrational, absorption (reflectance) and photoluminescence spectroscopies and their crystal structure was determined using single-crystal X-ray diffraction. B3LYP calculations were performed to support the interpretation and rationalization of the experimental results. The complexes, under UV irradiation, do not display the typical photodegradation of the β-diketonate ligands exhibiting, in turn, an unprecedented photostability during, at least, 10 h. During UV-A exposure (>330 nm), the emission intensities of both complexes increase drastically (∼20 times), whereas for t -Eu the emission quantum yield is enhanced at least 30-fold. A mechanism based on a photoclick trans-to-cis isomerization of both t- and c-bpete moieties was proposed to explain the abnormal photostability of these compounds, either in solid state or in solution. The experimental and computational results are consistent with a photostationary state involving the trans-to-cis isomerization of the bpete ligand under continuous UV-A exposure, which thus diverts the incident radiation from other deleterious photochemical or photophysical processes that cause the typical photobleaching behavior of chelate lanthanide complexes. This shielding mechanism could be extended to other ligands permitting the design of new lanthanide-based photostable systems under UV exposure for applications in lighting, sensing, and displays.