Luminescent chiral lanthanide(iii) complexes as potential molecular probes

Abstract

This perspective gives an introduction into the design of luminescent lanthanide(III)-containing complexes possessing chiral properties and used to probe biological materials. The first part briefly describes general principles, focusing on the optical aspect (i.e. lanthanide luminescence, sensitization processes) of the most emissive trivalent lanthanide ions, europium and terbium, incorporated into molecular luminescent edifices. This is followed by a short discussion on the importance of chirality in the biological and pharmaceutical fields. The second part is devoted to the assessment of the chiroptical spectroscopic tools available (typically circular dichroism and circularly polarized luminescence) and the strategies used to introduce a chiral feature into luminescent lanthanide(III) complexes (chiral structure resulting from a chiral arrangement of the ligand molecules surrounding the luminescent center or presence of chiral centers in the ligand molecules). Finally, the last part illustrates these fundamental principles with recent selected examples of such chiral luminescent lanthanide-based compounds used as potential probes of biomolecular substrates.

Synthesis, stereocontrol and structural studies of highly luminescent chiral tris-amidepyridyl-triazacyclononane lanthanide complexes

“…7,24 The CPL spectra of the  and  complexes of [Ln.L 1 ] were examined and showed mirror image behaviour ( Figure 6). In the latter case, the absolute configuration at each phosphorus is S, as is the case with this amide complex.…”

On the flocculation and re-dissolution of trivalent lanthanide metal ions by sodium dodecyl sulfate in aqueous solutions

“…Lanthanides have been used extensively as luminescent probes [13][14][15][16] in the investigation of metal-binding sites in biological materials [17][18][19][20], as well as in the study of surfactant association in solution [21,22]. In addition, systems of sodium dodecyl sulfate (SDS) micelles with lanthanide ions have been used for studying magnetic field effects on geminate pair recombination of radicals [23], or photo-induced emulsion polymerization [24], and are also of increasing interest in relation to the mesomorphism of lanthanide salts of anionic amphiphiles for materials applications [25,26].…”

Coordination chemistry of amide-functionalised tetraazamacrocycles: structural, relaxometric and cytotoxicity studies

“…[4][5][6][7][8][9][10] On the other hand, complexes of substituted polyazamacrocycles with lanthanides (e.g. Eu III , Tb III and Gd III ) have been shown to be excellent molecular probes for optical [11][12][13][14][15] and magnetic resonance imaging (MRI). [16][17][18][19] There are currently five gadolinium(III) complexes approved by the FDA for use as MRI contrast agents in the US.…”