Lanthanide Complexes Constructed by 2,2'-Oxybis(benzoic acid) and 1H-Imidazo[4,5-f][1,10]-phenanthroline: Fluorescence and Fluorescent Sensing for NH3†

doi:10.7503/cjcu20180009

Abstract

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

CLC Number:

O614
O641.4

TrendMD:

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†[J]. Chem. J. Chinese Universities, 2018, 39(12): 2611.

Figures/Tables 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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Lanthanide Complexes Constructed by 2,2'-Oxybis(benzoic acid) and 1H-Imidazo[4,5-f][1,10]-phenanthroline: Fluorescence and Fluorescent Sensing for NH³†

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