title: Density functional theory studies of actinide(III) motexafins (An-Motex2+, An = Ac, Cm, Lr). Structure, stability, and comparison with lanthanide(III) motexafins.
abstract: Newly developed relativistic energy-consistent 5f-in-core actinide pseudopotentials and corresponding (7s6p5d1f)/[5s4p3d1f] basis sets in the segmented contraction scheme, combined with density functional theory methods, have been used to study the molecular structure and chemical properties of selected actinide(III) motexafins (An-Motex2+, An = Ac, Cm, Lr). Structure and stability are discussed, and a comparison to the lanthanide(III) motexafins (Ln-Motex2+, Ln = La, Gd, Lu) is made. The actinide element is found to reside above the mean N5 motexafin plane, and the larger the cation, the greater the observed out-of-plane displacement. It is concluded that the actinium(III), curium(III), and lawrencium(III) cations are tightly bound to the macrocyclic skeleton, yielding stable structures. However, the calculated metal-ligand gas-phase binding energy for An-Motex2+ is about 1-2 eV lower than that of Ln-Motex2+, implying a lower stability of An-Motex2+ compared to Ln-Motex2+. Results including solvent effects imply that Ac-Motex2+ is the most stable complex in aqueous solution and should be the best candidate for experimentalists to get stable actinide(III) motexafin complexes.
authors.affiliation: Institut für Theoretische Chemie, Universität zu Köln, D-50939 Köln, Germany. x.cao@uni-koeln.de
authors.forename: Xiaoyan
authors.initials: X
authors.lastname: Cao
authors.forename: Quansong
authors.initials: Q
authors.lastname: Li
authors.forename: Anna
authors.initials: A
authors.lastname: Moritz
authors.forename: Zhizhong
authors.initials: Z
authors.lastname: Xie
authors.forename: Michael
authors.initials: M
authors.lastname: Dolg
authors.forename: Xuebo
authors.initials: X
authors.lastname: Chen
authors.forename: Weihai
authors.initials: W
authors.lastname: Fang