Chiroptical methods in a wide wavelength range for obtaining Ln3+ complexes with circularly polarized luminescence of practical interest. Issue 21 (18th May 2018)

• Record Type: Journal Article
• Authors: Górecki, Marcin; Carpita, Luca; Arrico, Lorenzo; Zinna, Francesco; Di Bari, Lorenzo
• Is Part Of: Dalton transactions. Volume 47:Issue 21(2018)
• Page Start: 7166
• Page End: 7177
• Publication Date: 2018-05-18
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt00865e
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Combining optical and chiroptical spectra from UV to IR in absorption and in emission gives a complete stereochemical fingerprint of chiral lanthanide complexes in solution. Surfing from one to another Ln further increases spectroscopic information. Abstract : We studied enantiopure chiral trivalent lanthanide (Ln 3+ = La 3+, Sm 3+, Eu 3+, Gd 3+, Tm 3+, and Yb 3+ ) complexes with two fluorinated achiral tris(β-diketonate) ligands (HFA = hexafluoroacetylacetonate and TTA = 2-thenoyltrifluoroacetonate), incorporating a chiral bis(oxazolinyl)pyridine ( PyBox ) unit as a neutral ancillary ligand, by the combined use of optical and chiroptical methods, ranging from UV to IR both in absorption and circular dichroism (CD), and including circularly polarized luminescence (CPL). Ultimately, all the spectroscopic information is integrated into a total and a chiroptical super-spectrum, which allows one to characterize a multidimensional chemical space, spanned by the different Ln 3+ ions, the acidity and steric demand of the diketone and the chirality of the PyBox ligand. In all cases, the Ln 3+ ions endow the systems with peculiar chiroptical properties, either allied to f–f transitions or induced by the metal onto the ligand. In more detail, we found that Sm 3+ complexes display interesting CPL features, which partly superimpose and partly integrate the more common Eu 3+ properties. Especially, in the context of security tags, the pair Sm/Eu may be a winning choice for chiroptical barcoding.