Hybrid materials based on novel 2D lanthanide coordination polymers covalently bonded to amine-modified SBA-15 and MCM-41: assembly, characterization, structural features, thermal and luminescence properties.
Three novel 2D coordination polymers [Tb2(μ4-L)2(μ-HL)(μ-HCOO)(DEF)]n(Tb-L), [Eu(μ4-L)(L)(H2O)2]n(Eu-L), and [Nd(μ4-L)(L)(H2O)2]n(Nd-L) were assembled from the corresponding lanthanide(iii) nitrates and 5 methoxy-(4-benzaldehyde)-1,3-benzenedicarboxylic acid (H2L) as a main multifunctional building block bearing carboxylate and aldehyde functional groups, using H2O/DEF {DEF = N,N-diethylformamide} as a reaction medium. The obtained coordination polymers were isolated as stable microcrystalline solids and fully characterized by elemental analysis, FT-IR spectroscopy, TGA, BET, PXRD, and single-crystal X-ray diffraction methods. Their structures feature intricate 2D metal-organic networks, which were topologically classified as underlying layers with the 4,6L26 (for Tb-L) or sql (for Eu-L and Nd-L) topologies. Besides, a novel series of mesoporous hybrid materials wherein the Tb-L, Eu-L, or Nd-L coordination polymers are covalently grafted into the amine-functionalized SBA-15-NH2or MCM-41-NH2matrices (via the formation of Schiff-base groups) was also synthesized and fully characterized. These hybrid materials show high thermal and photoluminescence stability, as well as remarkable chemical resistance to boiling water, and acidic or alkaline medium. Luminescent properties of the parent coordination polymers and derived hybrid materials are investigated in detail, showing that the latter combine the luminescent characteristics (intense green or red emissions and excellent stability) of lanthanide coordination polymers and structural features of ordered mesoporous silica molecular sieves. Moreover, light emitting devices were assembled, by coating the hybrid materials onto the surface of UV-LED bulbs, and showed excellent light emitting properties.
Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry, Laboratory of Special Function Materials and Structure Design, Ministry of Education, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China. fangr@lzu.edu.cn yanglz@lzu.edu.cn.
Jun
J
Wang
Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry, Laboratory of Special Function Materials and Structure Design, Ministry of Education, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China. fangr@lzu.edu.cn yanglz@lzu.edu.cn.
Wei
W
Dou
Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001, Lisbon, Portugal.
Alexander M
AM
Kirillov
Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry, Laboratory of Special Function Materials and Structure Design, Ministry of Education, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China. fangr@lzu.edu.cn yanglz@lzu.edu.cn.
Weisheng
http://orcid.org/0000-0003-4935-6879
W
Liu
Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry, Laboratory of Special Function Materials and Structure Design, Ministry of Education, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China. fangr@lzu.edu.cn yanglz@lzu.edu.cn.
Cailing
C
Xu
Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry, Laboratory of Special Function Materials and Structure Design, Ministry of Education, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China. fangr@lzu.edu.cn yanglz@lzu.edu.cn.
Ran
R
Fang
Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry, Laboratory of Special Function Materials and Structure Design, Ministry of Education, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China. fangr@lzu.edu.cn yanglz@lzu.edu.cn.
Lizi
L
Yang