Homometallic Uranium(VI) Phosphonoacetates Containing Interlayer Dipyridines

作者：Knope Karah E; Cahill Christopher L^*

来源：Inorganic Chemistry, 2009, 48(14): 6845-6851.

DOI：10.1021/ic9007735

Three organically templated uranium(VI) carboxyphosphonates, [C(10)H(10)N(2)][(UO(2))(3)(PPA)(2)(HPPA)(H(2)O)]center dot 3H(2)O (1), [C(12)H(12)N(2)][(UO(2))(3)(PPA)(2)(HPPA)(H(2)O)]center dot 2H(2)O (2), and [C(12)H(14)N(2)][(UO(2))(3)(PPA)(2)(HPPA)(H(2)O)]center dot 2H(2)O (3) have been prepared from hydrothermal reactions of UO(2)(NO(3))(2)center dot 6H(2)O and phosphonoacetic acid (H(2)O(3)PCH(2)CO(2)H, H(3)PPA) in the presence of 4,4'-dipyridyl, 1,2-bis(4-pyridyl)-ethylene and 1 2-bis(4-pyridyl)-ethane. The crystal structures of 1-3 are built from UO(7) units linked via phosphonoacetate molecules to form 2-dimensional [(UO(2))(3)(PPA)(2)(HPPA)(H(2)O)](2-) networks which are charge balanced by doubly protonated bipyridyl molecules. Interaction of the pyridyl molecules with other functionalities present in 1-3 result in relatively strong N-H center dot center dot center dot O (2.707-3.155 angstrom) and weaker C-H center dot center dot center dot O (2.948-3.237 angstrom) interactions that constitute the interlayer. Water-carboxylate O-H center dot center dot center dot O hydrogen bonding (2.548-2.675 angstrom) in 1-3 and pi-pi interactions (3.708 angstrom) between pyridyl rings in 2 also exist in these materials. Reported herein are the syntheses, structural characterization, and thermal and fluorescent behavior of 1-3.

• 出版日期2009-7-20