Rare earth metal–organic complexes constructed from hydroxyl and carboxyl modified arenesulfonate: syntheses, structure evolutions, and ultraviolet, visible and near-infrared luminescence. Issue 47 (17th November 2017)

• Record Type: Journal Article
• Authors: Xiao, Ying-Hui; Deng, Zhao-Peng; Zhu, Zhi-Biao; Huo, Li-Hua; Gao, Shan
• Is Part Of: Dalton transactions. Volume 46:Issue 47(2017)
• Page Start: 16493
• Page End: 16504
• Publication Date: 2017-11-17
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt03254d
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Thirty-eight rare earth metal-sulfonate complexes present seven typical structures and 17 of them exhibit diverse luminescence. Abstract : The reaction of 2-hydroxyl-4-carboxylbenzenesulfonic acid (H3 L) and rare earth (RE) metal nitrates together with two N-heterocyclic ligands gives rise to the formation of 38 complexes, namely, [La(H2 L)2 (ox)0.5 (H2 O)4 ] n ·2 n H2 O (1-La ) (ox = oxalate), [RE2 (H2 L)2 (ox)(H2 O)12 ]·2(H2 L)·8H2 O (2-RE ) (RE = Nd, Sm, Eu, Gd, Tb, Dy), [RE(SO4 )(H2 O)7 ]·(H2 L)·3H2 O (3-RE ) (RE = Ho, Er, Tm, Yb, Lu and Y), [RE(L)(H2 O)3 ] n · n H2 O (4-RE ) (RE = Er, Tm, Yb and Lu), [RE(L)(2, 2′-bipy)(H2 O)] n (5-RE ) (RE = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Y, 2, 2′-bipy = 2, 2′-bipyridine), [RE(L)(1, 10-phen)(H2 O)] n (6-RE ) (RE = La, Pr, Nd, Sm, Eu, 1, 10-phen = 1, 10-phenanthroline), and [RE(L′)(1, 10-phen)2 (H2 O)] n (7-RE ) (RE = Gd, Tb, Ho, Er, Yb and Lu, H3 L′ = 2-hydroxy-3-nitro-4-carboxybenzenesulfonic acid), which have been characterized by elemental analysis, IR, TG, PL, powder and single-crystal X-ray diffraction. Complexes1-La, 2-RE and3-RE present zigzag chain, di- and mono-nuclear structures, in which H2 L − acts as a counterion and monodentate and μ2 -bridging monoanions. For the three species, light RE metal cations tend to induce the formation of oxalate while heavy RE metal cations tend to induce the formation of sulfate. Complexes4-RE and5-RE exhibit layer structures incorporating helical chains, in which the L 3− trianion presents μ3 and μ4 coordination modes. Complexes6-RE containing light RE metal cations show layer structures incorporating helical chains, while complexes7-RE containing heavy RE metal cations have helical chain structures supported by the bridging of in situ generated L′ 3− . Remarkably, the in situ generated oxalates in1-La and2-RE, as well as the in situ generated L′ 3− in7-RE, also play a crucial role in determining the structures of these complexes. Structure evolutions make these complexes present various luminescent emissions. Complexes3-Tm, 3-Yb, 3-Lu, 3-Y and4-Lu exhibit ultraviolet emissions from 354 to 370 nm. Complexes1-La and6-La present blue emissions at 442 and 463 nm. Complexes2-Eu, 2-Tb, 5-Tb and7-Tb exhibit characteristic red and green emissions while the complex5-Y presents a green emission at 501 nm. Meanwhile, complexes2-Nd, 3-Yb, 4-Yb, 5-Nd, 6-Nd, and7-Yb show near-infrared (NIR) emissions. Moreover, 2-Eu, 2-Tb, 5-Tb, 7-Tb and5-Y show longer luminescence lifetimes from 390.47 to 1211.57 μs.