Synthesis of Novel Cd(Ⅱ) Metal-organic Framework for Highly Selective Detection of p-Nitroaniline†

doi:10.7503/cjcu20180579

Abstract

Abstract:

1,3,5-Tri(1H-benzo[d]imidazol-2-yl) benzene(TBB) and(2,5-dihydroxyterephthalic acid)(H₂dhtp) were used as linear ligands and Cd(Ⅱ) was used as the central node to construct a new type of chiral 3D metal-organic framework materials Cd(TBB)(dhtp)(1). The strong fluorescence emission property of complex 1 and the π-π interaction of the TBB ligand made it possible to detect nitro compounds and other pollutants by fluorescence. A further study showed that 4-nitroaniline had a high quenching ability for complex 1 and the limit of detection could be as low as 0.145 mg/L, indicating that complex 1 could be used as a highly efficient and highly selective detection probe for p-nitroaniline.

Key words: Metal-organic framework, Fluorescence detection, p-Nitroaniline

CLC Number:

O614.33

TrendMD:

FU Linjie,LUO Ran,WANG Shuhua,ZHANG Ning,CHEN Chao. Synthesis of Novel Cd(Ⅱ) Metal-organic Framework for Highly Selective Detection of p-Nitroaniline^†[J]. Chem. J. Chinese Universities, 2019, 40(3): 419.

Figures/Tables 9

Table 1 Crystal data and structure refinement parameters of compound 1

Empirical formula	C₃₅H₂₂CdN₆O₆	Crystal size	0.40 mm×0.30 mm×0.30 mm
Formula weight	735.00	θ Range for data collection/(°)	3.28—29.35
Crystal system	Hexagonal	Limiting indices	-23≤h≤26
Space group	P6(5)		-24≤k≤25
a/nm	1.89853(5)		-23≤l≤28
b/nm	1.89853(5)	Reflections collected/unique/R(int)	47142/10362/0.0764
c/nm	2.11139(9)	Data/restraints/parameters	10362/7/451
γ/(°)	120	Goodness-of-fit on F²	1.017
Volume/nm³	6.5907(4)	R₁[I>2σ(I)]	0.0591
Z	6	wR₂[I>2σ(I)]	0.1585
Calculated density/(Mg·m^-3)	1.111	R₁(all data)	0.0766
Absorption coefficient/mm^-1	0.538	wR₂(all data)	0.1695
F(000)	2220	Largest diff. peak and hole/(e·nm^-3)	1063, -443

Fig.1 Crystal structure of complex 1, molecular structures of SBUs and topological schematic of complex 1

Fig.2 π-π interaction(A) and hydrogen bonding(B) in the helical chain structure of complex 1Bond lengths are in nm.

Fig.3 Experimental and simulated PXRD patterns for complex 1

Fig.4 TG curve of complex 1

Fig.5 Fluorescence spectra of complex 1 in the presence of different nitroaromatic compounds(A) and the percentage of fluorescence quenching with different nitroaromatic compounds(B)(B) a. p-Nitroaniline; b. 2,4,6-trinitroaniline; c. 2,4-dinitrophenol; d. 2-nitrophenol; e. p-nitrophenol; f. p-nitrochlorobenzene; g. p-nitrotoluene; h. p-nitrobenzonitrile; i. Cd(TBB)/(dhtp).

Fig.6 Fluorescence spectra(A) and relative fluorescence intensity(B) of complex 1 with different concentrations of 4-nitroanilinec(4-Nitroaniline)/(mg·L-1) from a to w(A) and a—w(B): 0; 0.5; 0.75; 1; 1.25; 1.5; 1.75; 2; 2.25; 2.5; 2.75; 3; 3.25; 3.5; 3.75; 4; 4.5; 5; 5.5; 6; 6.5; 7; 7.5.

Fig.7 Stern-Volmer plot of complex 1 with different concentrations of 4-nitroaniline

Fig.8 Fluorescence intensity of complex 1 and different nitroaromatic compounds without(the left bars) or with(the right bars) 4-nitroanilinea. p-Nitroaniline; b. p-nitrobenzonitrile; c. p-nitrotoluene; d. p-nitrochlorobenzene; e. p-nitrophenol; f. 2-nitrophenol; g. 2,4,6-trinitroaniline; h. 2,4-dinitrophenol.

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