Isophthalato-based 2D coordination polymers of Eu(III), Gd(III), and Tb(III): enhancement of the terbium-centered luminescence through thiophene derivatization.
Isophthalato-based 2D coordination polymers of Eu(III), Gd(III), and Tb(III): enhancement of the terbium-centered luminescence through thiophene derivatization.
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DOI：
10.1021/ic048499b.s001
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发表时间：
2005
影响因子：
4.6
通讯作者：
Ana de Bettencourt-Dias
中科院分区：
文献类型：
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作者：
Ana de Bettencourt-Dias
我们在此展示了仅含间苯二甲酸或噻吩基间苯二甲酸配体的镧系离子配合物的首批实例。间苯二甲酸与Eu(3+)（1）和Tb(3+)（2）的配合物以及5 - 噻吩 - 3 - 基间苯二甲酸酯与Eu(3+)（3）、Gd(3+)（4）和Tb(3+)（5）的中等溶解性配合物通过凝胶结晶法被分离为单晶。X射线衍射研究证实了这些配合物的交联结构，对于噻吩基衍生物而言，这种结构导致其在普通溶剂中的溶解性较低。Eu(3+)的二维间苯二甲酸配合物（1）在C2/c空间群中结晶，其a = 22.154(4) Å，b = 12.649(3) Å，c = 15.921(3) Å，β = 112.34(3)°，V = 4126.7(14) ų；而同一配体的一维Tb(3+)配合物（2）在P2₁/c空间群中结晶，a = 11.921(2) Å，b = 10.838(2) Å，c = 17.499(4) Å，β = 92.44(3)°，V = 2258.9(8) ų。Eu(3+)（3）和Gd(3+)（4）的噻吩基间苯二甲酸配合物是二维的，在P2/n空间群中结晶，3的参数为a = 14.139(3) Å，b = 10.684(2) Å，c = 15.138(3) Å，β = 102.51(3)°，V = 2232.3(8) ų；4的参数为a = 14.1195(13) Å，b = 10.6594(10) Å，c = 15.1149(14) Å，β = 102.529(2)°，V = 2220.7(4) ų；而Tb(3+)配合物（5）也是二维的，在P空间群中结晶，a = 11.051(2) Å，b = 14.528(3) Å，c = 15.041(3) Å，α = 77.63(3)°，β = 87.86(3)°，γ = 83.51(3)°，V = 2343.48 ų。所有Eu(3+)和Tb(3+)的配合物在水溶液中都发光，其发光寿命和量子产率分别为123.8 ± 7.4 μs，0.14%（1）；475.1 ± 14.5 μs，3.58%（3）；129.3 ± 3.5 μs，0.19%（4）；以及213.9 ± 2.2 μs，7.46%（5）。
We present here the first examples of lanthanide ion complexes with only isophthalic acid or thiophenylisophthalic acid ligands. The complexes of isophthalic acid with Eu(3+) (1) and Tb(3+) (2) and the moderately soluble complexes of 5-thiophen-3-ylisophthalate with Eu(3+) (3), Gd(3+) (4), and Tb(3+) (5) were isolated as single crystals through gel crystallization. X-ray diffraction studies confirm the cross-linking structure of these complexes, which, in case of the thiophenyl derivatives, results in low solubility in common solvents. The two-dimensional isophthalato complex of Eu(3+) (1) crystallizes in the C2/c space group, with a = 22.154(4), b = 12.649(3), and c = 15.921(3) A, beta = 112.34(3) degrees, and V = 4126.7(14) A(3), while the one-dimensional Tb(3+) complex of the same ligand, 2, crystallizes in the space group P2(1)/c with a = 11.921(2), b = 10.838(2), and c = 17.499(4) A, beta = 92.44(3) degrees, and V = 2258.9(8) A(3). The thiophenylisophthalato complexes of Eu(3+) (3) and Gd(3+) (4) are two-dimensional and crystallize in the P2/n space group with parameters for 3 of a = 14.139(3), b = 10.684(2), and c = 15.138(3) A, beta = 102.51(3) degrees, and V = 2232.3(8) A(3) and parameters for 4 of a = 14.1195(13), b = 10.6594(10), and c = 15.1149(14) A, beta = 102.529(2) degrees, and V = 2220.7(4) A(3), while the Tb(3+) complex, 5, also two-dimensional, crystallizes in the P space group with a = 11.051(2), b = 14.528(3), and c = 15.041(3) A, alpha = 77.63(3), beta = 87.86(3), and gamma = 83.51(3) degrees, and V = 2343.48 A(3). All complexes of Eu(3+) and Tb(3+) luminesce in aqueous solution, and the luminescence lifetimes and quantum yields are 123.8 +/- 7.4, 0.14% (1), 475.1 +/- 14.5, 3.58% (3), 129.3 +/- 3.5, 0.19% (4), and 213.9 +/- 2.2 micros, 7.46% (5).