(2-羧基苯氧基)苯-1,2-二羧酸构筑的镧系配合物对苯甲醛和阳离子的荧光传感

doi:10.7503/cjcu20160126

摘要/Abstract

摘要：

采用水热法合成了5个稀土配合物[Sm₂(bdbc)₂(phen)₄](1)和[Ln(bdbc)(phen)(H₂O)][Ln=Eu(2), Gd(3), Tb(4), Dy(5), bdbc=(2-羧基苯氧基)苯-1,2-二羧酸根, phen=1,10-邻菲啰啉]. 配合物1是双核分子, 通过氢键和C—H…π作用进一步构筑成一维超分子结构; 配合物2~5是同构的一维双螺旋结构, 通过氢键和C—H…π作用进一步构筑成三维超分子结构. 配合物1, 2, 4和5呈现了Sm³⁺, Eu³⁺, Tb³⁺和Dy³⁺离子的特征发射, 分别对应于Sm³⁺离子的⁴G_5/2→⁶H_J_/2(J=5, 7, 9)、 Eu³⁺离子的⁵D₀→⁷F_J(J=1—4)、 Tb³⁺离子的⁵D₄→⁷F_J(J=6, 5, 4, 3)和Dy³⁺离子的⁴F_5/2→⁶H_J_/2(J=15, 13)跃迁. 对配合物4的荧光性质进行了表征, 结果表明, 配合物4可用作荧光探针以检测阳离子和苯甲醛.

关键词: 稀土配合物, 荧光探针, 阳离子, 苯甲醛

Abstract:

Five lanthanide-organic frameworks, [Sm₂(bdbc)₂(phen)₄](1) and [Ln(bdbc)(phen)·(H₂O)][Ln=Eu(2), Gd(3), Tb(4), Dy(5), bdbc=3-(2-carboxy-phenoxy)phthalicate, phen=1,10-phenanthroline], have been synthesized and determined by X-ray single-crystal diffraction. Complex 1 is a binuclear molecule and forms a one-dimensional(1D) supramolecular architecture via hydrogen and C—H…π bonds. Complexes 2—5 are isostructural and display a one-dimensional(1D) chain structure, which form a three-dimensional(3D) supramolecular architecture via hydrogen and C—H…π bonds. Complexes 1, 2, 4 and 5 present the characteristic emission of Sm³⁺, Eu³⁺, Tb³⁺ and Dy³⁺, which are attributed to ⁴G_5/2→⁶H_J_/2(J=5, 7, 9) transitions of Sm³⁺, ⁵D₀→⁷F_J(J=1—4) transitions of Eu³⁺, ⁵D₄→⁷F_J(J=6, 5, 4, 3) transitions of Tb³⁺, ⁴F_5/2→⁶H_J_/2(J=15, 13) transitions of Dy³⁺, respectively. Furthermore, the luminescence properties of complex 4 were investigated. The results show that complex 4 may be used as a fluorescent probe to detect cation in aqueous solution and benzaldehyde.

Key words: Lanthanide complex, Fluorescent probe, Cation, Benzaldehyde

中图分类号:

O614
O641.4

TrendMD:

董高云, 李睿, 樊婷婷, 李佳佳, 李夏. (2-羧基苯氧基)苯-1,2-二羧酸构筑的镧系配合物对苯甲醛和阳离子的荧光传感. 高等学校化学学报, 2016, 37(8): 1421.

DONG Gaoyun,LI Rui,FAN Tingting,LI Jiajia,LI Xia. Luminescence Sensing of Benzaldehyde and Cation of 3-(2-Carboxy-phenoxy)-phthalicate-based Lanthanide Complexes^†. Chem. J. Chinese Universities, 2016, 37(8): 1421.

图/表 11

Table 1 Crystallographic data of complexes 1—5

Compound	1	2	3	4	5
Empirical formula	C₇₈H₄₆N₈O₁₄Sm₂	C₂₇H₁₇N₂O₈Eu	C₂₇H₁₇N₂O₈Gd	C₂₇H₁₇N₂O₈Tb	C₂₇H₁₇N₂O₈Dy
Formula weight	1619.93	649.39	654.67	656.34	659.92
Temperature/K	296(2)	296(2)	296(2)	296(2)	296(2)
Crystal system	Monoclinic	Monoclinic	Monoclinic	Monoclinic	Monoclinic
Space group	C2/c	P2₁/n	P2₁/n	P2₁/n	P2₁/n
a/nm	2.79501(11)	1.17504(5)	1.17519(4)	1.1732(2)	1.17249(4)
b/nm	1.33737(5)	1.04560(4)	1.04434(4)	1.0427(2)	1.04125(4)
c/nm	2.30816(15)	2.01377(8)	2.01048(7)	2.0085(4)	2.00662(7)
β/(°)	121.4560(10)	96.7414(11)	96.8519(11)	96.86(3)	96.8906(10)
V/nm³	7.3599(6)	2.45706(17)	2.44983(15)	2.4394(9)	2.43210(15)
Z	4	4	4	4	4
D_c/(Mg·m^-3)	1.462	1.755	1.775	1.787	1.802
Absorption coefficient/mm^-1	1.649	2.608	2.763	2.955	3.128
F(000)	3224	1280	1284	1288	1292
Crystal size/mm	0.328×0.069×0.056	0.411×0.359×0.189	0.339×0.204×0.156	0.296×0.230×0.101	0.382×0.116×0.091
θ range for data collection /(°)	2.98—24.51	3.19—27.49	3.19—27.55	3.451—25.098	3.20—27.50
Limiting indices	-36≤h≤36, -17≤k≤17, -29≤l≤30	-14≤h≤13, -12≤k≤12, -24≤l≤24	-14≤h≤13, -12≤k≤12, -23≤l≤23	-14≤h≤13, -12≤k≤12, -23≤l≤23	-13≤h≤13, -12≤k≤12, -23≤l≤23
Reflections collected/unique	75545/6539	31331/4367	31544 / 4354	32542 / 4341	31358 / 4324
R_int	0.0920	0.0256	0.0280	0.0291	0.0326
Completeness(%)	99.6	99.8	99.8	99.8	99.8
Data/restraints/parameters	8519/0/460	4367/1/353	4354/1/353	4331/1/353	4324/1/353
Goodness-of-fit on F²	1.037	1.064	1.037	1.082	1.076
Final R indices[I>2σ(I)]	R₁=0.1082, wR₂=0.0991	R₁=0.0225, wR₂=0.0471	R₁=0.0240, wR₂=0.0434	R₁=0.0229, wR₂=0.0441	R₁=0.0288, wR₂=0.0459
R indices(all data)	R₁=0.0440, wR₂=0.0833	R₁=0.0194, wR₂ =0.0451	R₁=0.0191, wR₂=0.0411	R₁=0.0182, wR₂=0.0420	R₁=0.0210, wR₂=0.0432
CCDC No.	1052818	1052814	1052845	1052846	1052875

Table 1 Crystallographic data of complexes 1—5

Compound	1	2	3	4	5
Empirical formula	C₇₈H₄₆N₈O₁₄Sm₂	C₂₇H₁₇N₂O₈Eu	C₂₇H₁₇N₂O₈Gd	C₂₇H₁₇N₂O₈Tb	C₂₇H₁₇N₂O₈Dy
Formula weight	1619.93	649.39	654.67	656.34	659.92
Temperature/K	296(2)	296(2)	296(2)	296(2)	296(2)
Crystal system	Monoclinic	Monoclinic	Monoclinic	Monoclinic	Monoclinic
Space group	C2/c	P2₁/n	P2₁/n	P2₁/n	P2₁/n
a/nm	2.79501(11)	1.17504(5)	1.17519(4)	1.1732(2)	1.17249(4)
b/nm	1.33737(5)	1.04560(4)	1.04434(4)	1.0427(2)	1.04125(4)
c/nm	2.30816(15)	2.01377(8)	2.01048(7)	2.0085(4)	2.00662(7)
β/(°)	121.4560(10)	96.7414(11)	96.8519(11)	96.86(3)	96.8906(10)
V/nm³	7.3599(6)	2.45706(17)	2.44983(15)	2.4394(9)	2.43210(15)
Z	4	4	4	4	4
D_c/(Mg·m^-3)	1.462	1.755	1.775	1.787	1.802
Absorption coefficient/mm^-1	1.649	2.608	2.763	2.955	3.128
F(000)	3224	1280	1284	1288	1292
Crystal size/mm	0.328×0.069×0.056	0.411×0.359×0.189	0.339×0.204×0.156	0.296×0.230×0.101	0.382×0.116×0.091
θ range for data collection /(°)	2.98—24.51	3.19—27.49	3.19—27.55	3.451—25.098	3.20—27.50
Limiting indices	-36≤h≤36, -17≤k≤17, -29≤l≤30	-14≤h≤13, -12≤k≤12, -24≤l≤24	-14≤h≤13, -12≤k≤12, -23≤l≤23	-14≤h≤13, -12≤k≤12, -23≤l≤23	-13≤h≤13, -12≤k≤12, -23≤l≤23
Reflections collected/unique	75545/6539	31331/4367	31544 / 4354	32542 / 4341	31358 / 4324
R_int	0.0920	0.0256	0.0280	0.0291	0.0326
Completeness(%)	99.6	99.8	99.8	99.8	99.8
Data/restraints/parameters	8519/0/460	4367/1/353	4354/1/353	4331/1/353	4324/1/353
Goodness-of-fit on F²	1.037	1.064	1.037	1.082	1.076
Final R indices[I>2σ(I)]	R₁=0.1082, wR₂=0.0991	R₁=0.0225, wR₂=0.0471	R₁=0.0240, wR₂=0.0434	R₁=0.0229, wR₂=0.0441	R₁=0.0288, wR₂=0.0459
R indices(all data)	R₁=0.0440, wR₂=0.0833	R₁=0.0194, wR₂ =0.0451	R₁=0.0191, wR₂=0.0411	R₁=0.0182, wR₂=0.0420	R₁=0.0210, wR₂=0.0432
CCDC No.	1052818	1052814	1052845	1052846	1052875

Fig.1 Coordination environment of Sm3+ in complex 1(A) and 1D chain structure of complex 1 via the hydrogen bonds and C—H…π interactions(B)

Fig.2 Coordination environment of Eu3+ in complex 2(A), 1D chain structure(B) and 3D supramolecular structure via the hydrogen bonds and C—H…π interactions(C) of complex 2

Fig.3 Emission spectra of complex 3(a) and free ligands phen(b) and bdbc(c)

Fig.4 Excitation(B, D) and emission(A, C) spectra of complexes 2(A, B) and 4(C, D)(B) a. λex=352 nm; b. λex=397 nm; (D) a. λex=350 nm; b. λex=380 nm.

Fig.5 Emission spectra(A) and the 5D4→7F5 transition intensities(B) of complex 4 in the presence of different cations(10-2 mol/L) a. H2O; b. K+; c. Ca2+; d. Li+; e. Mg2+; f. Na+; g. Pb2+; h. Ba2+; i. Zn2+; j. Al3+; k. Cd2+; l. Ni2+; m. Cu2+; n. Ag+; o. Co2+; p. Cr2+; q. Fe3+.

Fig.6 Emission spectra(A) and the 5D4→7F5 transition intensities(B) of complex 4 in the presence of different concentrations of Co2+(λex=350 nm) c(Co2+)/(mol·L-1): a. 0; b. 5×10-6; c. 1×10-5; d. 1×10-4; e. 1×10-3; f. 5×10-3; g. 5×10-2.

Fig.7 Emission spectra(A) and 5D4→7F5 transition intensities(B) of complex 4 in the presence of different concentrations of Fe3+(λex=350 nm) c(Fe3+)/(mol·L-1): a. 0; b. 5×10-6; c. 1×10-5; d. 1×10-4; e. 1×10-3; f. 5×10-3; g. 5×10-2.

Fig.8 Emission spectra(A, B) and 5D4→7F5 transition intensity(insets) of complex 4 dispersed in different solvents(λex=350 nm) (A) a. EtOAc; b. acetone; c. benzene. (B) a. Benzene; b. dichloromethane; c. methanol; d. formamide; e. dimethylbenzene; f. acetonitrile; g. DMF; h. formaldeltyde; i. benzaldehyde.

Fig.9 Emission spectra(A) and 5D4→7F5 transition intensity(B) of complex 4 dispersed in EtOAc with different concentrations of benzaldehyde(λex=350 nm) c(Benzaldehyde)/(mol·L-1): a. 10-6; b. 5×10-5; c. 10-4; d. 2×10-4; e. 3×10-4; f. 5×10-4; g. 6×10-4; h. 8×10-4.

Fig.10 TG curves of complexes 1—5(a—e)

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