title: Effects of Ligand Geometry on the Photophysical Properties of Photoluminescent Eu(III) and Sm(III) 1-Hydroxypyridin-2-one Complexes in Aqueous Solution.
abstract: A series of 10 tetradentate 1-hydroxy-pyridin-2-one (1,2-HOPO) ligands and corresponding eight-coordinated photoluminescent Eu(III) and Sm(III) complexes were prepared. Generally, the ligands differ by the linear (nLI) aliphatic linker length, from 2 to 8 methylene units between the bidentate 1,2-HOPO chelator units. The photoluminescent quantum yields (Φtot) were found to vary with the linker length, and the same trend was observed for the Eu(III) and Sm(III) complexes. The 2LI and 5LI bridged complexes are the brightest (Φtotxε). The change in ligand wrapping pattern between 2LI and 5LI complexes observed by X-ray diffraction (XRD) is further supported by density functional theory (DFT) calculations. The bimodal Φtot trends of the Eu(III) and Sm(III) complexes are rationalized by the change in ligand wrapping pattern as the bridge (nLI) is increased in length.
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Department of Chemistry, University of California , Berkeley, California 94720-1460, United States.
authors.forename: Lena J
authors.initials: LJ
authors.lastname: Daumann
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Department of Chemistry, University of California , Berkeley, California 94720-1460, United States.
authors.forename: David S
authors.initials: DS
authors.lastname: Tatum
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Department of Chemistry, University of California , Berkeley, California 94720-1460, United States.
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Andolina
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Department of Chemistry, University of California , Berkeley, California 94720-1460, United States.
authors.forename: Joseph I
authors.initials: JI
authors.lastname: Pacold
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Department of Chemistry, University of California , Berkeley, California 94720-1460, United States.
authors.forename: Anthony
authors.initials: A
authors.lastname: D'Aléo
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Department of Chemistry, University of California , Berkeley, California 94720-1460, United States.
authors.forename: Ga-lai
authors.initials: GL
authors.lastname: Law
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Department of Chemistry, University of California , Berkeley, California 94720-1460, United States.
authors.forename: Jide
authors.initials: J
authors.lastname: Xu
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Department of Chemistry, University of California , Berkeley, California 94720-1460, United States.
authors.forename: Kenneth N
authors.initials: KN
authors.lastname: Raymond
mesh_terms: D066241:Carbon-13 Magnetic Resonance Spectroscopy; D005063:Europium / Q000737:chemistry*; D008024:Ligands; D049449:Luminescence; D066244:Proton Magnetic Resonance Spectroscopy; D012493:Samarium / Q000737:chemistry*; D012996:Solutions; D014867:Water / Q000737:chemistry
chemical_list: D008024:Ligands; D012996:Solutions; D014867:Water; D012493:Samarium; D005063:Europium