Anion-directed self-assembly of lanthanide-notp compounds and their fluorescence, magnetic, and catalytic properties

Reactions of 1,4,7-triazacyclononane-1,4,7-triyl-tris(methylenephosphonic acid) notpH(6), C(9)H(18)N(3)(PO(3)H(2))3] with different lanthanide salts result in four types of Ln-notp compounds: Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(NO(3))(H(2)O)].4H2O (1), Ln = Eu (1 Eu), Gd (1 Gd), Tb (1 Tb)], Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(H2O)]Cl.3H2O (2) Ln = Eu (2 Eu), Gd (2 Gd), Tb (2 Tb)], Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(H2O)]ClO4.8H2O, (3) Ln = Eu (3 Eu), Gd (3 Gd)], and Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(H2O)]ClO4.3H2O (4), Ln = Gd (4 Gd), Tb (4 Tb)]. Compounds within each type are isostructural. In compounds 1, dimers of {Ln2(notpH4)2(NO3)2(H2O)2} are found, in which the two lanthanide atoms are connected by two pairs of O-P-O and one pair of mu-O bridges. The NO3- ion serves as a bidentate terminal ligand. Compounds 2 contain similar dimeric units of {Ln2(notpH4)2(H2O)2} that are further connected by a pair of O-P-O bridges into an alternating chain. The Cl- ions are involved in the interchain hydrogen-bonding networks. A similar chain structure is also found in compounds 3; in this case, however, the chains are linked by ClO4- counterions through hydrogen-bonding interactions, forming an undulating layer in the (011) plane. These layers are fused through hydrogen-bonding interactions, leading to a three-dimensional supramolecular network with large channels in the 100] direction. Compounds 4 show an interesting brick-wall-like layer structure in which the neighboring lanthanide atoms are connected by a pair of O-P-O bridges. The ClO4- counterions and the lattice water molecules are between the layers. In all compounds the triazamacrocyclic nitrogen atoms are not coordinated to the Ln(III) ions. The anions and the pH are believed to play key roles in directing the formation of a particular structure. The fluorescence spectroscopic properties of the Eu and Tb compounds, magnetic properties of the Gd compounds, and the catalytic properties of 4 Gd were also studied.