title: Supramolecular Assembly of Molecular Rare-Earth-3,5-Dichlorobenzoic Acid-2,2':6',2″-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior.
abstract: The syntheses and crystal structures of 16 new rare-earth (RE = La(3+)-Y(3+))-3,5-dichlorobenzoic acid-terpyridine molecular materials characterized via single-crystal and powder X-ray diffraction are reported. These 16 complexes consist of four unique structure types ranging from molecular dimers (La(3+) and Ce(3+)) to tetramers (Pr(3+)-Y(3+)) as one moves across the RE(3+) series. This structural evolution is accompanied by subsequent changes in modes of supramolecular assembly (halogen bonding, halogen-π, halogen-halogen, and π-π interactions). Solid-state visible and near-infrared lifetime measurements were performed on complexes 6 (Sm(3+)), 7 (Eu(3+)), 9 (Tb(3+)), 10 (Dy(3+)), 11 (Ho(3+)), 12 (Er(3+)), and 14 (Yb(3+)), and characteristic emission was observed for all complexes except 11. Lifetime data for 11, 12, and 14 suggest sensitization by the terpy antenna does occur in near-infrared systems, although not as efficiently as in the visible region. Additionally, direct current magnetic susceptibility measurements were taken for complexes 10 (Dy(3+)) and 12 (Er(3+)) and showed dominant ferromagnetic behavior.
authors.affiliation: Department of Chemistry, The George Washington University , 800 22nd Street, Northwest, Washington, D.C. 20052, United States.
authors.forename: Korey P
authors.initials: KP
authors.lastname: Carter
authors.affiliation: Department of Chemistry, The George Washington University , 800 22nd Street, Northwest, Washington, D.C. 20052, United States.
authors.forename: Kara E
authors.initials: KE
authors.lastname: Thomas
authors.affiliation: School of Chemistry, Cardiff University , Main Building, Cardiff, Cymru/Wales CF10 3AT, U.K.
authors.forename: Simon J A
authors.initials: SJ
authors.lastname: Pope
authors.affiliation: Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, ON, Canada K1N 6N5.
authors.forename: Rebecca J
authors.initials: RJ
authors.lastname: Holmberg
authors.affiliation: Department of Chemistry, Howard University , 525 College Street, Northwest, Washington, D.C. 20059, United States.
authors.forename: Ray J
authors.initials: RJ
authors.lastname: Butcher
authors.affiliation: Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, ON, Canada K1N 6N5.
authors.forename: Muralee
authors.initials: M
authors.lastname: Murugesu
authors.affiliation: Department of Chemistry, The George Washington University , 800 22nd Street, Northwest, Washington, D.C. 20052, United States.
authors.forename: Christopher L
authors.initials: CL
authors.lastname: Cahill