title: Diverse lanthanide coordination polymers tuned by the flexibility of ligands and the lanthanide contraction effect: syntheses, structures and luminescence.
abstract: Two new flexible exo-bidentate ligands were designed and synthesized, incorporating different backbone chain lengths bearing two salicylamide arms, namely 2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(N-benzylbenzamide) (L(I)) and 2,2'-(2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)bis(N-benzylbenzamide) (L(II)). These two structurally related ligands are used as building blocks for constructing diverse lanthanide polymers with luminescent properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, TGA analysis, X-ray powder diffraction, and IR spectroscopy, ten new coordination polymers have been determined using X-ray diffraction analysis. All the coordination polymers exhibit the same metal-to-ligand molar ratio of 2 : 3. L(I), as a bridging ligand, reacts with lanthanide nitrates forming two different types of 2D coordination complexes: herringbone framework {[Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)](∞) (Ln = La (1), and Pr (2), m = 1, 2)} as type I,; and honeycomb framework {[Ln(2)(NO(3))(6)(L(I))(3)·nCH(3)OH](∞) (Ln = Nd (3), Eu (4), Tb (5), and Er (6), n = 0 or 3)} as type II, which change according to the decrease in radius of the lanthanide. For L(II), two distinct structure types of 1D ladder-like coordination complexes were formed with decreasing lanthanide radii: [Ln(2)(NO(3))(6)(L(II))(3)·2C(4)H(8)O(2)](∞) (Ln = La (7), Pr (8), Nd (9)) as type III, [Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)·nCH(3)OH](∞) (Ln = Eu (10), Tb (11), and Er (12), m, n = 2 or 0) as type IV. The progressive structural variation from the 2D supramolecular framework to 1D ladder-like frameworks is attributed to the varying chain length of the backbone group in the flexible ligands. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were also investigated in detail.
authors.affiliation: Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China.
authors.forename: Xiaoyan
authors.initials: X
authors.lastname: Zhou
authors.forename: Yanling
authors.initials: Y
authors.lastname: Guo
authors.forename: Zhaohua
authors.initials: Z
authors.lastname: Shi
authors.forename: Xueqin
authors.initials: X
authors.lastname: Song
authors.forename: Xiaoliang
authors.initials: X
authors.lastname: Tang
authors.forename: Xiong
authors.initials: X
authors.lastname: Hu
authors.forename: Zhentong
authors.initials: Z
authors.lastname: Zhu
authors.forename: Pengxuan
authors.initials: P
authors.lastname: Li
authors.forename: Weisheng
authors.initials: W
authors.lastname: Liu
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D028581:Lanthanoid Series Elements / Q000138:chemical synthesis / Q000737:chemistry*; D008024:Ligands; D049449:Luminescence; D008958:Models, Molecular; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*; D012457:Salicylamides / Q000138:chemical synthesis / Q000737:chemistry
chemical_list: D056831:Coordination Complexes; D028581:Lanthanoid Series Elements; D008024:Ligands; D011108:Polymers; D012457:Salicylamides; C031060:salicylamide