Two- to One-Dimensional: Radii-Dependent Self-Assembly Crystal Structures and Luminescent Properties of Lanthanide Coordination Polymers with an Amide Type Semirigid Bridging Ligand

• Published in: Crystal growth & design Vol. 11; no. 9; pp. 4205 - 4212
• Main Authors: Yan, Xuhuan, Li, Yafei, Wang, Qiong, Huang, Xiaoguang, Zhang, Ye, Gao, Cunji, Liu, Weisheng, Tang, Yu, Zhang, Hongrui, Shao, Yongliang
• Format: Journal Article
• Language: English
• Published: Washington,DC American Chemical Society 07.09.2011
• Subjects: Amorphous materials, glasses and other disordered solids; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Materials science; Optical properties and condensed-matter spectroscopy and other interactions of matter with particles and radiation; Organic compounds; Other materials; Photoluminescence; Physics; Specific materials; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Honeycomb lattices; Energy levels; Molecular structure; Polychelate; Porous materials; Amides; Resonance energy; Gadolinium; Nitrates; XRD; Dysprosium; Topology; Europium additions; Triplet state; Self-assembly; Monocrystals; Rare earths; Ligands; Europium; Erbium; Crystal structure
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/cg200816f

Lanthanide coordination polymers {[Ln2L3(NO3)6]·nH2O} n [Ln = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7), and Er (8), where n = 0 except for 1 with n = 4 and 2 with n = 7] have been assembled using lanthanide nitrates and an amide type semirigid bridging ligand, 1,3-bis{[(2′-benzylaminoformyl)phenoxyl]methylbenzene (L), as building blocks. The crystal structures of the complexes {[Pr2L3(NO3)6] n ·4H2O} n (1), {[Nd2L3(NO3)6]·7H2O} n (2), [Sm2L3(NO3)6] n (3), [Eu2L3(NO3)6] n (4), [Tb2L3(NO3)6] n (6), and [Er2L3(NO3)6] n (8)} were determined by single-crystal X-ray diffraction. Interestedly, 1 and 2 demonstrate unusual lanthanide porous noninterpenetrated honeycomb-like (6,3) topology frameworks, while 3, 4, 6, and 8 exhibit novel one-dimensional linear coordination polymeric structures. Their structural variations are attributed to lanthanide contraction effects. The luminescent properties of Sm(III), Eu(III), Tb(III), and Dy(III) complexes are also investigated in detail. The lowest triplet state (T1) energy level of this ligand matches better to the lowest resonance energy levels of Tb(III) and Dy(III) than Eu(III) and Sm(III) ions.