Coumarin-lanthanide based compounds with SMM behavior and high quantum yield luminescence†
Coumarin-based lanthanide complexes of general formula [Ln(coum)3(phen)(H2O)x]·yH2O (Ln-phen, x = 0,1, 0 ≤ y ≤ 1.5; phen = 1,10-phenanthroline; coum = 3-acetyl-4-hydroxylato-coumarin; Ln = Eu, Tb, Dy, Tm) and [Ln(coum)3(batho)]·0.7EtOH (Ln-batho, batho = 4,7-diphenyl-1,10-phenanthroline; Ln = Eu, Tb, Dy, Tm) were synthesized. The magnetic relaxation and photoluminescence behavior of these complexes was compared with that of the related compounds [Ln(coum)3(EtOH)(H2O)]·EtOH (Ln-coum), so as to investigate the effects of incorporating a second chromophore, either the phen or batho ligand, to the original coordination scaffold, provided with three coumarin (coum) ligands. Slow relaxation of the magnetization under H = 0 with moderate activation energies was observed for the Dy-phen (U/kB = 99.1 K) and Dy-batho (U/kB = 67.1 K) compounds, whereas Tb analogues presented field-induced single molecule magnet (SMM) behavior, with U/kB = 11.7 K (16.6 K@3 kOe) for Tb-phen (Tb-batho), respectively. Luminescent emission in the visible range was observed for all the Ln-coumarin based compounds upon ligand sensitization, with high quantum yields of 45 (40%) for Eu-phen (Eu-batho) compounds and 65–76–58% for Tb-coum, phen, batho analogues. Sensitization is mainly provided by the coumarin ligand having the energy difference ΔE between its triplet state T1 and the lanthanide emitting level closest to the optimum, while the second ligand can play either a synergistic or competing sensitizing role. The Tb-phen/batho compounds presented simultaneously SMM and luminescent behavior, with excellent values of the bifunctional figure of merit (ηSMM–QY ∼ 1000% K). The reported compounds represent a new class of bifunctional materials with potential interesting application in various fields.