Structure impact in antenna effect of novel upper rim substituted tetra-1,3-diketone calix[4]arenes on Tb(III) green and Yb(III) NIR-luminescence

Two novel calix[4]arene macrocyclic ligands functionalized with four 1,3-diketone groups at the upper and hydroxyl (3) or propyloxy-groups (6) at the lower rims were synthesized and characterized using NMR, IR spectroscopy, mass spectrometry, and elemental analysis. UV-vis spectrophotometry and ESI mass spectrometry studies indicate 1:1 complex formation of ligands 3 and 6 with Ln(III) (Ln=Tb, Yb) in alkaline DMF solutions resulted from coordination of Ln(III) with 1,3-diketonate groups. Luminescence study of Ln(III) complexes with 3 and 6 reveals significant difference in antenna effects of their deprotonated forms on both Tb(III)- and Yb(III)-centered luminescence. Comparison of ligand-centered emission for ligands 3 and 6 points to the latter as more efficient antenna for Tb(III) and Yb(III). Different conformational behavior of ligands 3 and 6 in alkaline media is assumed as a reason for the experimentally observed difference in sensitization pathways in Ln(III) complexes with 3 and 6.

133