title: Ytterbium(III) porpholactones: β-lactonization of porphyrin ligands enhances sensitization efficiency of lanthanide near-infrared luminescence.
abstract: The near-infrared (NIR) luminescence efficiency of lanthanide complexes is largely dependent on the electronic and photophysical properties of antenna ligands. Although porphyrin ligands are efficient sensitizers of lanthanide NIR luminescence, non-pyrrolic porphyrin analogues, which have unusual symmetry and electronic states, have been much less studied. In this work, we used porpholactones, a class of β-pyrrolic-modified porphyrins, as ligands and investigated the photophysical properties of lanthanide porpholactones Yb-1 a-5 a. Compared with Yb porphyrin complexes, the porpholactone complexes displayed remarkable enhancement of NIR emission (50-120 %). Estimating the triplet-state levels of porphyrin and porpholactone in Gd complexes revealed that β-lactonization of porphyrinic ligands lowers the ligand T1 state and results in a narrow energy gap between this state and the lowest excited state of Yb(3+) . Transient absorption spectra showed that Yb(III) porpholactone has a longer transient decay lifetime at the Soret band than the porphyrin analogue (30.8 versus 17.0 μs). Thus, the narrower energy gap and longer lifetime arising from β-lactonization are assumed to enhance NIR emission of Yb porpholactones. To demonstrate the potential applications of Yb porpholactone, a water-soluble Yb bioprobe was constructed by conjugating glucose to Yb-1 a. Interestingly, the NIR emission of this Yb porpholactone could be specifically switched on in the presence of glucose oxidase and then switched off by addition of glucose. This is the first demonstration that non-pyrrolic porphyrin ligands enhance the sensitization efficiency of lanthanide luminescence and also display switchable NIR emission in the region of biological analytes (800-1400 nm).
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare-Earth Materials Chemistryand Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (P. R. China), Fax: (+86) 1062767034.
authors.forename: Xian-Sheng
authors.initials: XS
authors.lastname: Ke
authors.forename: Bo-Yan
authors.initials: BY
authors.lastname: Yang
authors.forename: Xin
authors.initials: X
authors.lastname: Cheng
authors.forename: Sharon Lai-Fung
authors.initials: SL
authors.lastname: Chan
authors.forename: Jun-Long
authors.initials: JL
authors.lastname: Zhang
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry; D005947:Glucose / Q000737:chemistry; D007783:Lactones / Q000737:chemistry*; D008024:Ligands; D011166:Porphyrins / Q000737:chemistry*; D011789:Quantum Theory; D019265:Spectroscopy, Near-Infrared; D013816:Thermodynamics; D014867:Water / Q000737:chemistry; D015018:Ytterbium / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D007783:Lactones; D008024:Ligands; D011166:Porphyrins; D014867:Water; D005947:Glucose; D015018:Ytterbium
keywords: biosensors; lanthanides; luminescence; porphyrinoids; ytterbium