The reaction of 2-hydroxyl-4-carboxylbenzenesulfonic acid (H₃L) and rare earth (RE) metal nitrates together with two N-heterocyclic ligands gives rise to the formation of 38 complexes, namely, [La(H₂L)₂(ox)_0.5(H₂O)₄]_n·2nH₂O (1-La) (ox = oxalate), [RE₂(H₂L)₂ (ox)(H₂O)₁₂]·2(H₂L)·8H₂O (2-RE) (RE = Nd, Sm, Eu, Gd, Tb, Dy), [RE(SO₄)(H₂O)₇]·(H₂L)·3H₂O (3-RE) (RE = Ho, Er, Tm, Yb, Lu and Y), [RE(L)(H₂O)₃]_n·nH₂O (4-RE) (RE = Er, Tm, Yb and Lu), [RE(L)(2,2′-bipy)(H₂O)]_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)(H₂O)]_n (6-RE) (RE = La, Pr, Nd, Sm, Eu, 1,10-phen = 1,10-phenanthroline), and [RE(L′)(1,10-phen)₂(H₂O)]_n (7-RE) (RE = Gd, Tb, Ho, Er, Yb and Lu, H₃L′ = 2-hydroxy-3-nitro-4-carboxybenzenesulfonic acid), which have been characterized by elemental analysis, IR, TG, PL, powder and single-crystal X-ray diffraction. Complexes 1-La, 2-RE and 3-RE present zigzag chain, di- and mono-nuclear structures, in which H₂L⁻ 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. Complexes 4-RE and 5-RE exhibit layer structures incorporating helical chains, in which the L³⁻ trianion presents μ₃ and μ₄ coordination modes. Complexes 6-RE containing light RE metal cations show layer structures incorporating helical chains, while complexes 7-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 in 1-La and 2-RE, as well as the in situ generated L′³⁻ in 7-RE, also play a crucial role in determining the structures of these complexes. Structure evolutions make these complexes present various luminescent emissions. Complexes 3-Tm, 3-Yb, 3-Lu, 3-Y and 4-Lu exhibit ultraviolet emissions from 354 to 370 nm. Complexes 1-La and 6-La present blue emissions at 442 and 463 nm. Complexes 2-Eu, 2-Tb, 5-Tb and 7-Tb exhibit characteristic red and green emissions while the complex 5-Y presents a green emission at 501 nm. Meanwhile, complexes 2-Nd, 3-Yb, 4-Yb, 5-Nd, 6-Nd, and 7-Yb show near-infrared (NIR) emissions. Moreover, 2-Eu, 2-Tb, 5-Tb, 7-Tb and 5-Y show longer luminescence lifetimes from 390.47 to 1211.57 μs.

中文翻译：

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由羟基和羧基改性的芳烃磺酸盐构成的稀土金属有机配合物：合成，结构演变以及紫外线，可见光和近红外光的发光

2-羟基-4-羧基苯磺酸（H ₃ L）和稀土（RE）金属硝酸盐与两个N-杂环配体的反应导致形成38个络合物，即[La（H ₂ L）₂（ox）_0.5（H ₂ O）₄ ] _n ·2 n H ₂ O（1-La）（ox =草酸盐），[RE ₂（H ₂ L）₂（ox）（H ₂ O）₁₂ ]·2 （H ₂ L）·8H ₂ O（2-RE）（RE = Nd，Sm，Eu，Gd，Tb，Dy），[RE（SO ₄）（H ₂O）₇ ]·（H ₂ L）·3H ₂ O（3-RE）（RE = Ho，Er，Tm，Yb，Lu和Y），[RE（L）（H ₂ O）₃ ] _n · n H ₂ O（4-RE）（RE = Er，Tm，Yb and Lu），[RE（L）（2,2'-bipy）（H ₂ O）] _n（5-RE）（RE = La， Pr，Nd，Sm，Eu，Gd，Tb，Dy，Ho和Y，2,2'-bipy = 2,2'-bipyridine），[RE（L）（1,10-phen）（H ₂ O） ] _n（6-RE）（RE = La，Pr，Nd，Sm，Eu，1,10-phen = 1,10-菲咯啉）和[RE（L'）（1,10-phen）₂（H ₂ O）] _n（7-RE）（RE = Gd，Tb，Ho，Er，Yb和Lu，H ₃ L'= 2-羟基-3-硝基-4-羧基苯磺酸），通过元素分析，IR，TG， PL，粉末和单晶X射线衍射。络合物1的La，2-RE和3-RE本Z字形链，二-和单核结构，其中H ₂大号^-作为抗衡离子和单齿和μ _2个-bridging一价阴离子。对于这三个物种，轻稀土金属阳离子倾向于诱导草酸盐的形成，而重稀土金属阳离子倾向于诱导硫酸盐的形成。配合物4-RE和5-RE掺入螺旋链，在将L表现出层结构的^3-三价阴离子呈现μ ₃和μ _4种的配位模式。含有轻稀土金属阳离子的配合物6-RE显示出包含螺旋链的层结构，而含有重稀土金属阳离子的配合物7-RE具有由原位生成的L' ^3-的桥联支撑的螺旋链结构。值得注意的是，在1-La和2-RE中原位生成的草酸盐，以及在7-RE中原位生成的L' ^3-在确定这些复合物的结构方面也起着至关重要的作用。结构的演变使这些复合物呈现出各种发光。配合物3-Tm，3-Yb，3-Lu，3-Y和4-Lu显示出354至370 nm的紫外线发射。配合物1-La和6-La在442和463 nm处呈现蓝色发射。配合物2-Eu，2-Tb，5-Tb和7-Tb呈现特征性的红色和绿色发射，而配合物5-Y显示501 nm的绿色发射。同时，络合物2-Nd，3-Yb，4-Yb，5-Nd，6-Nd和7-Yb显示近红外（NIR）发射。此外，2-Eu，2-Tb，5-Tb，7-Tb和5-Y的发光寿命更长，从390.47到1211.57μs。