Synthesis, Crystal Structure and Fluorescent Properties of Transition Metal Complexes Constructed with 2-(3'-Carboxyphenoxy)benzoic Acid and N-Donor Ligands†

doi:10.7503/cjcu20180347

Abstract

Abstract:

Taking 2-(3'-carboxyphenoxy)benzoic acid(2,3'-H₂oba), 1,3-bis(4-pyridyl)-propane(DPP) and 1,4-bis(1,2,4-triazole-1-)butane(BTB) as ligands, two transition metal complexes Cd(2,3'-oba)(DPP)(1) and Zn(2,3'-oba)(BTB)_0.5(2) were obtained by hydrothermal method. Complex 1 is a two-dimensional network structure, the coordination environment of the central Cd²⁺ is {CdO₄N₂}, the 2,3'-oba ligand and the DPP ligand link Cd²⁺ into Cd²⁺-2,3'-oba-Cd²⁺-DPP helical chains by bidentate chelating and monodentate bridging modes, respectively. Complex 1 is linked by intermolecular hydrogen bonding and self-assembled into a three-dimensional supramolecular structure. Complex 2 is a three-dimensional framework structure, and the central Zn²⁺ adopts a five-coordinated distortion quadrilateral cone configuration {ZnO₄N}. The 2,3'-oba ligand links the adjacent Zn²⁺ as a bidentate chelate and a bidentate bridge to form a two-dimensional network layer. The BTB molecule bridges the Zn²⁺ and connects adjacent network layers to form a three-dimensional structure. Fluorescence spectroscopy indicates that complexes 1 and 2 have maximum emission at 437 nm and 359 nm, respectively, both are derived from the π^*-π transition of the ligand. The broad-spectrum pesticide mesotrione has a significant quenching effect on the fluorescence intensity of complex 2, thus complex 2 can be used as a chemical sensor for detecting mesotrione.

Key words: Transition metal complex, 2-(3'-Carboxyphenoxy)benzoic acid, Crystal structure, Fluorescence

CLC Number:

O614

TrendMD:

LI Zheng, LI Rui, LI Xia. Synthesis, Crystal Structure and Fluorescent Properties of Transition Metal Complexes Constructed with 2-(3'-Carboxyphenoxy)benzoic Acid and N-Donor Ligands^†[J]. Chem. J. Chinese Universities, 2018, 39(11): 2363.

Figures/Tables 13

Table 1 Crystallographic data of complexes 1 and 2

Complex	1	2
Empirical formula	C₂₇H₂₂CdN₂O₅	C₁₈H₁₄N₃O₅Zn
Formula weight	566.87	417.69
Temperature/K	293(2)	296(2)
Crystal system	Monoclinic	Monoclinic
Space group	P2₁/c	C2/c
a/nm	1.0091(2)	1.6159(5)
b/nm	1.3008(3)	1.3546(7)
c/nm	2.0610(6)	1.6657(8)
α/(°)	90	90
β/(°)	116.83(2)	113.59(2)
γ/(°)	90	90
V/nm³	2.4141(10)	3.3418(31)
Z	4	8
D_c/(Mg·m^-3)	1.560	1.660
Absorption coefficient/mm^-1	0.945	1.507
F(000)	1144	1704
Crystal size/mm	0.44×0.31×0.22	0.37×0.33×0.29
θ range for data collection/(°)	3.32—27.63	2.89—27.56
Limiting indices	-13≤h≤13, -16≤k≤16, -26≤l≤26	-20≤h≤20, -17≤k≤17, -21≤l≤21
Reflections collected	36889	25433
R_int	0.0599	0.0849
Data/restraints/parameters	5569/0/316	3853/8/244
Goodness-of-fit on F²	1.015	1.026
Final R indices [I>2σ(I)]	R₁=0.0471, wR₂=0.0996	R₁=0.0494, wR₂=0.0886
R indices(all data)	R₁=0.1140, wR₂=0.1220	R₁=0.1004, wR₂=0.1028
CCDC No.	1437942	1817762

Table 2 Selected bond lengths(nm) and angles(°) for complex 1*

Cd1—O4	0.2291(3)	Cd1—O5	0.2352(3)		Cd1—O1A	0.2326(4)
Cd1—N1	0.2312(4)	Cd1—N2	0.2296(3)		Cd1—O2A	0.2373(4)
O4—Cd1—N2	93.79(13)	O4—Cd1—O2A		93.50(16)	N1—Cd1—O1A		85.48(14)
N2—Cd1—N1	91.38(13)	N1—Cd1—O2A		131.47(15)	N2—Cd1—O5		134.43(13)
N2—Cd1—O1A	116.67(17)	O5—Cd1—O2A		123.62(17)	O1A—Cd1—O5		108.88(17)
O4—Cd1—O5	55.22(11)	O4—Cd1—N1		134.98(13)	N2—Cd1—O2A		86.60(16)
N1—Cd1—O5	90.89(12)	O4—Cd1—O1A		130.13(17)	O1A—Cd1—O2A		53.49(14)

Table 3 Selected bond lengths(nm) and angles(°) for complex 2

Zn1—O3	0.1987(2)	Zn1—N3	0.2025(2)		Zn1—O4
Zn1—O1	0.2002(3)	Zn1—O2	0.2303(2)
O3—Zn1—O1	108.62(10)	O4—Zn1—O2		144.29(10)	O4—Zn1—N3	93.46(9)
O1—Zn1—O4	95.22(9)	O3—Zn1—O4		117.10(9)	O1—Zn1—O2	60.02(10)
O1—Zn1—N3	145.90(11)	O3—Zn1—N3		96.40(10)	N3—Zn1—O2	95.33(10)
O3—Zn1—O2	96.21(9)

Fig.1 Coordination environment of Cd(Ⅱ)(A), 2D structure(B), hydrogen bond(C) and 3D structure(D) of complex 1All hydrogen atoms are omitted for clarity; symmetry code: A: x-1, y, z.

Fig.2 L-helix chain(A), helix structure(B) and R-helix chain(C) of complex 1All hydrogen atoms are omitted for clarity; symmetry code: A: x-1, y, z.

Fig.3 Coordination environment of Zn2+(A), 2D structure(B) and 3D structure(C) of complex 2All hydrogen atoms are omitted for clarity.

Fig.4 Emission spectra of complex 2(a), BTB(b), DPP(c), 2,3'-H2oba(d) and complex 1(e)For complex 1, λex=369 nm; for complex 2, λex=319 nm.

Fig.5 Emission spectra(A) and fluorescence intensity at 437 nm(B) of complex 1 in various solventsSolvent from a to j: methanol; water; ethanol; DMF; ethyl acetate; DMSO; chloroform; acetonitrile;dichloromethane; acetone.

Fig.6 Emission spectra(A) and fluorescence intensity at 359 nm(B) of complex 2 in various solventsSolvent from a to j: methanol; water; ethanol; DMF; ethyl acetate; DMSO; chloroform; acetonitrile; dichloromethane; acetone.

Fig.7 PXRD patterns of complex 2(a) and complex 2 after being dipped in methanol for 24 h(b)

Fig.8 Emission spectra and peak intensity(inset) of complex 2 dispersed in methanol containing hymexazol(b), carbendazim(c), tebuconazole(d) and mesotrione(e)a. Blank.

Fig.9 Emission spectra and peak intensity(inset) of complex 2 dispersed in methanol solvent containing mesotrione with various concentrationsc(Mesotrione)/(mol·L-1) for a—j: 0, 2.5×10-7, 5×10-7, 10-6, 2.5×10-6, 5×10-6, 10-5, 2.5×10-5, 5×10-5, 1×10-4.

Fig.10 TGA and DTA curves of complexes 1(A) and 2(B)

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