由2,2'-联苯醚二甲酸和1H-咪唑并[4,5-f][1,10]-邻菲罗啉构筑的稀土配合物的荧光光谱及对氨的荧光传感

doi:10.7503/cjcu20180009

摘要/Abstract

摘要：

采用水热法合成了5个新的配合物[Ln₂(2,2'-Hoba)₆(IP)₂]{Ln=Eu(1), Tb(2), 2,2'-H₂oba=2,2'-联苯醚二甲酸, IP=1H-咪唑并[4,5-f][1,10]-邻菲罗啉}, [Ln₂(2,2'-oba)₃(IP)][Ln=Eu(3), Tb(4)]和[Eu₂(2,2'-oba)₃(TPP)(H₂O)](5){TPP=四吡啶[2,3-a:3',2'-c:2″,3″-h:3″',2″'-j]夹二氮蒽}, 并通过X射线单晶衍射、元素分析和红外光谱等对其结构和组成进行了确认. 配合物1和2是双核分子结构, 配合物3和4是1D链状结构, 配合物5是3D结构. 利用荧光光谱法研究了配合物1~5与NH₃ 的识别作用. 结果表明, NH₃对配合物1~5都有一定的荧光猝灭作用, 猝灭率为82.05%~97.49%. 同时研究了配合物1与NH₃和金属阳离子(Ca²⁺, K⁺, Mg²⁺, Na⁺, Zn²⁺, Cu²⁺, Cr³⁺, Ba²⁺, Al³⁺, Mn²⁺, Ni²⁺和Pb²⁺)的荧光作用. 实验结果表明, 在生理环境(pH=4~8)下, 配合物1具有良好的稳定性, NH₃使配合物1的荧光性能减弱, 同时NH₃对配合物1的荧光猝灭性不受pH的影响, 说明配合物1对NH₃具有较好的灵敏性. 在配合物1-NH₃的体系中, 加入并增加Zn²⁺, Al³⁺或Cr³⁺离子浓度, 在波长为430~510 nm范围内出现了新的发射宽峰, 并且在618 nm处的峰强度先增强后减弱. 这是Zn²⁺(Al³⁺或Cr³⁺)、 NH₃与配合物1共同作用的有力证明. 配合物1作为识别NH₃的荧光探针显示出较好的灵敏性, 同时一些金属阳离子对其探针行为有影响.

关键词: 稀土配合物, 荧光, NH₃识别, 金属阳离子

Abstract:

New complexes [Ln₂(2,2'-Hoba)₆(IP)₂]{Ln=Eu(1), Tb(2), 2,2'-H₂oba=2,2'-oxybis(benzoic acid), IP=1H-imidazo[4,5-f][1,10]-phenanthroline}, [Ln₂(2,2'-oba)₃(IP)](Ln=Eu(3), Tb(4)] and [Eu₂(2,2'-oba)₃(TPP)(H₂O)](5){TPP=tetrapyrido[2,3-a:3',2'-c:2″,3″-h:3″',2″'-j]phenazine} were synthesized under hydrothermal condition and characterized by X-ray single crystal diffraction(XRD), IR spectroscopy and elemental analysis. Complexes 1 and 2 have dinuclear molecular structures, complexes 3 and 4 reveal 1D line structure and complex 5 features a 3D structure. The recognition of complexes 1—5 for NH₃ was discussed with method of fluorescence spectroscopy. The results showed that they had highly sensitivity for NH₃ via a fluorescence quenching mechanism, with the quenching rates of 82.05%—97.49%. The recognition of complex 1 for NH₃ and some metal ions(Ca²⁺, K⁺, Mg²⁺, Na⁺, Zn²⁺, Cu²⁺, Cr³⁺, Ba²⁺, Al³⁺, Mn²⁺, Ni²⁺and Pb²⁺) was studied. Luminescent investigation revealed that complex 1 could detect NH₃ with relatively high sensitivity in contrast to some metal ions, even at pH=4.0—8.0. The respective addition of some cations(Zn²⁺, Al³⁺or Cr³⁺) into the complex 1-NH₃ system resulted in obvious fluorescent variation at 618 nm, with the fluorescent intensity at 618 nm increasing rapidly and then decreasing and a new peak occurring at 430—510 nm. Because of the synergy influence of NH₃ and Zn²⁺(Al³⁺or Cr³⁺), if Zn²⁺(Al³⁺or Cr³⁺) solution was added into 1-NH₃ system, the emission peak among 430—510 nm came into being. This showed that complex 1, NH₃ and Zn²⁺(Al³⁺or Cr³⁺) had some combined action. The primary results showed that complex 1 had some sensitive recognition capability for NH₃, and this action was impacted by some metal ions.

Key words: Lanthanide complex, Fluorescence, Ammonia recognition, Metal ion

中图分类号:

O614
O641.4

TrendMD:

张德春, 许奇炜, 李夏. 由2,2'-联苯醚二甲酸和1H-咪唑并[4,5-f][1,10]-邻菲罗啉构筑的稀土配合物的荧光光谱及对氨的荧光传感. 高等学校化学学报, 2018, 39(12): 2611.

ZHANG Dechun,XU Qiwei,LI Xia. Lanthanide Complexes Constructed by 2,2'-Oxybis(benzoic acid) and 1H-Imidazo[4,5-f][1,10]-phenanthroline: Fluorescence and Fluorescent Sensing for NH³†. Chem. J. Chinese Universities, 2018, 39(12): 2611.

图/表 15

Table 1 Crystal data and structural refinement for complexes 1—5

Complex	1	2	3	4	5
Empirical formula	C₁₁₀H₇₀N₈O₃₀Eu₂	C₁₁₀H₇₀N₈O₃₀Tb₂	C₅₅H₃₂N₄O₁₅Eu₂	C₅₅H₃₂N₄O₁₅Tb₂	C₆₆H₃₈N₆O₁₆Eu₂
Formula weight	2287.66	2301.58	1292.77	1306.69	1474.94
Crystal system	Triclinic	Triclinic	Triclinic	Triclinic	Monoclinic,
Space group	P $1 ˉ$	P $1 ˉ$	P $1 ˉ$	P $1 ˉ$	C2/c
a/nm	1.15131(5)	1.14885(5)	1.31535(12)	1.28091(10)	2.84806(10)
b/nm	1.38342(6)	1.38288(6)	1.39415(13)	1.42179(11)	1.40143(5)
c/nm	1.70498(8)	1.70231(8)	1.45396(13)	1.49624(11)	2.97567(10)
α/(°)	113.4990(10)	113.4240(10)	73.313(2)	74.132(2)	90
β/(°)	93.4370(10)	93.4800(10)	72.018(3)	67.660(2)	108.9160(10)
γ/(°)	93.1820(10)	92.9840(10)	84.328(3)	81.947(2)	90
V/nm³	2.47653(19)	2.46845(19)	2.4291(4)	2.4224(3)	11.2355(7)
Z	1	1	2	2	8
D_c/(Mg·m^-3)	1.534	1.548	1.767	1.791	1.744
μ/mm^-1	1.342	1.509	2.636	2.974	2.294
F(000)	1152	1156	1272	1280	5840
Crystal size/mm³	0.234×0.139× 0.132	0.211×0.107× 0.067	0.391×0.232× 0.063	0.227×0.126× 0.101	0.300×0.204× 0.152
θ Range for data collection/(°)	2.95—25.01	2.95—25.01	2.97—25.01	2.90—25.01	2.91—27.55
Limiting indices	-13≤h≤13, -16≤k≤16, -20≤l≤20	-13≤h≤13, -16≤k≤16, -20≤l≤20	-15≤h≤15, -16≤k≤16, -17≤l≤17	-15≤h≤15, -16≤k≤16, -17≤l≤17	-36≤h≤36, -17≤k≤18, -38≤l≤38
Reflections collected/unique	44087/8720 [R(int)=0.0650]	43696/8696 [R(int)=0.0822]	40881/8573 [R(int)=0.0930]	39331/8520 [R(int)=0.1195]	85920/12923 [R(int)=0.0974]
Data/restraints/parameters	8720/108/718	8696/127/675	8573/0/685	8520/0/685	12923/0/812
Largest difference peak and hole/(e·nm^-3)	1356 and -883	1353 and -779	1416 and -1360	1527 and -1000	1568 and -883
Goodness-of-fit on F²	1.045	1.082	1.066	1.069	1.043
Final R indices[I>2σ(I)]	R₁=0.0447, wR₂=0.1190	R₁=0.0522, wR₂=0.1210	R₁=0.0370, wR₂=0.0906	R₁=0.0462, wR₂=0.0996	R₁=0.0415, wR₂=0.0996
R indices(all data)	R₁=0.0571, wR₂=0.1321	R₁=0.0780, wR₂=0.1385	R₁=0.0504, wR₂=0.1073	R₁=0.0794, wR₂=0.1178	R₁=0.0585, wR₂=0.1066
CCDC No.	1587904	1587905	1587906	1587909	1587910

Table 1 Crystal data and structural refinement for complexes 1—5

Complex	1	2	3	4	5
Empirical formula	C₁₁₀H₇₀N₈O₃₀Eu₂	C₁₁₀H₇₀N₈O₃₀Tb₂	C₅₅H₃₂N₄O₁₅Eu₂	C₅₅H₃₂N₄O₁₅Tb₂	C₆₆H₃₈N₆O₁₆Eu₂
Formula weight	2287.66	2301.58	1292.77	1306.69	1474.94
Crystal system	Triclinic	Triclinic	Triclinic	Triclinic	Monoclinic,
Space group	P $1 ˉ$	P $1 ˉ$	P $1 ˉ$	P $1 ˉ$	C2/c
a/nm	1.15131(5)	1.14885(5)	1.31535(12)	1.28091(10)	2.84806(10)
b/nm	1.38342(6)	1.38288(6)	1.39415(13)	1.42179(11)	1.40143(5)
c/nm	1.70498(8)	1.70231(8)	1.45396(13)	1.49624(11)	2.97567(10)
α/(°)	113.4990(10)	113.4240(10)	73.313(2)	74.132(2)	90
β/(°)	93.4370(10)	93.4800(10)	72.018(3)	67.660(2)	108.9160(10)
γ/(°)	93.1820(10)	92.9840(10)	84.328(3)	81.947(2)	90
V/nm³	2.47653(19)	2.46845(19)	2.4291(4)	2.4224(3)	11.2355(7)
Z	1	1	2	2	8
D_c/(Mg·m^-3)	1.534	1.548	1.767	1.791	1.744
μ/mm^-1	1.342	1.509	2.636	2.974	2.294
F(000)	1152	1156	1272	1280	5840
Crystal size/mm³	0.234×0.139× 0.132	0.211×0.107× 0.067	0.391×0.232× 0.063	0.227×0.126× 0.101	0.300×0.204× 0.152
θ Range for data collection/(°)	2.95—25.01	2.95—25.01	2.97—25.01	2.90—25.01	2.91—27.55
Limiting indices	-13≤h≤13, -16≤k≤16, -20≤l≤20	-13≤h≤13, -16≤k≤16, -20≤l≤20	-15≤h≤15, -16≤k≤16, -17≤l≤17	-15≤h≤15, -16≤k≤16, -17≤l≤17	-36≤h≤36, -17≤k≤18, -38≤l≤38
Reflections collected/unique	44087/8720 [R(int)=0.0650]	43696/8696 [R(int)=0.0822]	40881/8573 [R(int)=0.0930]	39331/8520 [R(int)=0.1195]	85920/12923 [R(int)=0.0974]
Data/restraints/parameters	8720/108/718	8696/127/675	8573/0/685	8520/0/685	12923/0/812
Largest difference peak and hole/(e·nm^-3)	1356 and -883	1353 and -779	1416 and -1360	1527 and -1000	1568 and -883
Goodness-of-fit on F²	1.045	1.082	1.066	1.069	1.043
Final R indices[I>2σ(I)]	R₁=0.0447, wR₂=0.1190	R₁=0.0522, wR₂=0.1210	R₁=0.0370, wR₂=0.0906	R₁=0.0462, wR₂=0.0996	R₁=0.0415, wR₂=0.0996
R indices(all data)	R₁=0.0571, wR₂=0.1321	R₁=0.0780, wR₂=0.1385	R₁=0.0504, wR₂=0.1073	R₁=0.0794, wR₂=0.1178	R₁=0.0585, wR₂=0.1066
CCDC No.	1587904	1587905	1587906	1587909	1587910

Fig.1 Coordination environment of Eu(Ⅲ) ions(A) and dinuclear molecular structure in complex 1(B)

Fig.2 Coordination modes of the 2,2'-H2oba2- ligand

Fig.3 Coordination environment of Eu(Ⅲ) ions(A), 1D chain structure along the b axis(B) and the 2D framework of complex 3 via feeble interactions(C)

Fig.4 Coordination environment of Eu(III) ions(A)and the 3D framework of complex 5(B)

Fig.5 Excitation(A) and emission(B) spectra of complexes 1—5(a—e) in solid state at room temperature

Fig.6 Fluorescence intensity(5D0→7F2 or 5D4→7F5) changes(A) and the quenching rate(B) of complexes 1—5 upon addition of NH3 at room temperaturec(NH3)=10 mmol/L, m(complex)=10 mg, V(NH3)=10 mL. (A) a. complex 1; b. complex 1+NH3; c. complex 2; d. complex 2+NH3; e. complex 3; f. compound 3+NH3; g. complex 4; h. complex 4+NH3; i. complex 5; j. complex 5+NH3.

Fig.7 Fluorescence spectra changes of complex 1 upon addition of NH3 and mental ions at room temperaturec(NH3)=c(metal ion)=5 mmol/L, V=10 mL, m(complex 1)=10 mg. λex=368 nm, λem=618 nm.

Fig.8 Effect of NH3 on the fluorescence spectra of complex 1(A), histogram of fluorescence intensity and NH3 concentration(B)c(NH3)=0, 0.1, 0.5, 1.0, 5.0, 10, 50 mmol/L(a—g), V(NH3)=10 mL, m(complex 1)=10 mg, T=25 ℃, λex=368 nm, λem=618 nm.

Fig.9 Relationship between lg(F0/F-1) and lgc(NH3)

Fig.10 Emission spectra of complex 1-NH3 in the presence of different metal ionsc(NH3)=c(metal ion)=5 mmol/L, V=10 mL, m(complex 1)=10 mg, T=25 ℃, λex=368 nm, λem=618 nm.

Fig.11 Effect of Zn2+ on the fluorescence spectra of complex 1-NH3c(Zn2+)=0—50 mmol/L, c(NH3)=20 mmol/L, V(Zn2+)=10 mL, m(complex 1)=10 mg, T=25 ℃, λex=368 nm, λem=618 nm.

Fig.12 Effect of Al3+ on the fluorescence spectra of complex 1-NH3 c(Al3+)=0—50 mmol/L, c(NH3)=5 mmol/L, V=10 mL, m(complex 1)=10 mg, T=25 ℃, λex=368 nm, λem=618 nm.

Fig.13 Effect of Cr3+ on the fluorescence spectra of complex 1-NH3c(Cr3+)=0—50 mmol/L, c(NH3)=5 mmol/L, V=10 mL, m(complex 1)=10 mg, T=25 ℃, λex=368 nm, λem=618 nm.

Fig.14 Relationship between fluorescence intensity of complex 1 and 1-NH3 with different pH values

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