Synthesis, Structure and Recognition Properties of Macrocyclic Crown Ethers with Oxadiazole †

doi:10.7503/cjcu20190317

Abstract

Abstract:

A series of macrocyclic crown ethers containing oxadiazole groups were synthesized and their single crystals were obtained. Their structures were characterized by nuclear magnetic resonance(NMR), high resolution electrospray ionization mass spectroscopy(HRESI-MS) and X-ray single crystal diffraction. The single crystal X-ray diffraction revealed that 2,3,11,12-dibenzo-4,7,10,16-tetraoxa-14,15-diazabicyclo[11.2.1]-hexadecane-13,15-diene(2) belonged to orthorhombic crystal system with space group Pna2₁, 2,3,14,15-dibenzo-4,7,10,13,19- pentaoxa-17,18-diazabicyclo[14.2.1]-nonadecane-16,18-diene(3) belongs to monoclinic crystal system with space group C2/c and 2,3,17,18-dibenzo-4,7,10,13,16,22-hexaoxa-20,21-diazabicyclo[17.2.1]-docosadecane-19,21-diene(4) belonged to orthorhombic crystal system with space group Pbca. Three crown ethers were all connected to form a three-dimensional supramolecular structure by C—H…O or C—H…N hydrogen bond intramolecular and π-π stacking. The bonding behaviors of 2,5-bis[2-(2-methoxyethoxy)phenyl]-1,3,4-oxadiazole(1) and crown ethers 2—4 with different sizes to metal ions Li ⁺, Na ⁺, K ⁺, Rb ⁺, Mg ²⁺ and Ca ²⁺ was determined by fluorescence spectroscopy. The results showed that open-chain crown ether 1 and macrocyclic crown ether 4 exhibited fluorescence quenching behavior and good bon-ding ability and selectivity on alkaline earth metal Ca ²⁺. While crown ether 2 showed good bonding ability to Na ⁺ and K ⁺and poor Na ⁺/K ⁺ selectivity.

Key words: 1,3,4-Dioxazole, Crown ether, Cationic recognition, Crystal structure, Fluorescence spectroscopy

CLC Number:

O626

TrendMD:

TIAN Xia,YANG Fuqun,YUAN Wei,ZHAO Lei,YAO Lei,ZHEN Xiaoli,HAN Jianrong,LIU Shouxin. Synthesis, Structure and Recognition Properties of Macrocyclic Crown Ethers with Oxadiazole ^†[J]. Chem. J. Chinese Universities, 2020, 41(3): 490.

Figures/Tables 9

Scheme 1 Structures and synthsis routes of the target molecules

Crown ether	1	2	3	4
Empirical formula	C₂₀H₂₂N₂O₅	C₁₈H₁₆N₂O₄	C₂₀H_20.38N₂O_5.19	C₂₂H₂₄N₂O₆
Formula weight	370.40	324.33	371.76	412.43
Temperature/K	293(2)	113(2)	113(2)	113(2)
Crystal system	Monoclinic	Orthorhombic	Monoclinic	Orthorhombic
Space group	P2₁/n	Pna2₁	C2/c	Pbca
a/nm	0.77264(15)	0.83211(17)	2.9681(6)	0.127122(18)
b/nm	1.3886(3)	1.1948(2)	0.89442(18)	0.83364(12)
c/nm	1.6911(3)	1.5156(3)	2.9443(6)	3.7002(5)
α/(°)	90.00	90.00	90.00	90.00
β/(°)	96.42(3)	90.00	91.61(3)	90.00
γ/(°)	90.00	90.00	90.00	90.00
Volume/nm³	0.784	1.506.8(5)	7.813(3)	3.9212(10)
Z	4	4	16	8
F(000)	408	680	3134	1744
Crystal size/mm^-3	0.16×0.14×0.10	0.18×0.16×0.14	0.20×0.18×0.12	0.22×0.20×0.1
2θ range/(°)	2.42—27.87	2.17—27.51	2.48—25.02	1.10—27.88
Index range	-9≤h≤10, -13≤k≤18, -20≤l≤22	-10≤h≤10, -15≤k≤15, -19≤l≤19	-35≤h≤24, -10≤k≤10, -34≤l≤35	-6≤h≤9, -16≤k≤16, -19≤l≤20
Data/restraint/parameter	4290/0/246	3450/1/217	6832/317/566	4665/0/271
Final R indices [I >2σ(I)], wR₂(all data)	R₁=0.0403, wR₂=0.1043	R₁=0.0387, wR₂=0.0933	R₁=0.0825, wR₂=0.2257	R₁=0.0415, wR₂=0.1042

Fig.1 Molecular structures of crown ethers 1—4

Fig.2 Packing diagram of crown ethers 1—4

Crown ether	D—H…A	d(D—H)	d(H A)	d(D…A)	∠DHA
1	C5—H5…N2^a	0.093	0.262	0.33846(17)	140
	C20—H20B…O1^b	0.096	0.251	0.33451(17)	146
2	C11—H11A…O3^c	0.097	0.247	0.3409(2)	163
	C11—H11A…O3^d	0.097	0.259	0.2904(2)	100
3	C35—H35A…N4^e	0.093	0.248	0.3398(3)	169
4	C14—H14b…O4^f	0.099	0.258	0.35623(17)	171
	C15—H15B…N2 ^g	0.099	0.262	0.31511(18)	114

Crown ether	Stability constant(lgK_s)
Crown ether	Li⁺	Na⁺	K⁺	Rb⁺	Mg²⁺	Ca²⁺
1	$b$	6.58	$b$	5.72	5.30	14.69
2	$b$	6.72	6.81	$b$	$b$	6.35
3	4.44	5.37	$b$	5.85	$b$	5.26
4	6.45	6.49	$b$	$b$	1.83	5.20

Crown ether	Stability constant(lgK_s)
Crown ether	Li⁺	Na⁺	K⁺	Rb⁺	Mg²⁺	Ca²⁺
1	$b$	6.58	$b$	5.72	5.30	14.69
2	$b$	6.72	6.81	$b$	$b$	6.35
3	4.44	5.37	$b$	5.85	$b$	5.26
4	6.45	6.49	$b$	$b$	1.83	5.20

Fig.3 Fluorescence spectra of crown ether 1(1.0×10-6 mol/L) in the presence of differeat concentrations of sodium perchlorate(A) and calcium perchlorate(B) in CH3CN (A) 106c(sodium perchlorate)/(mol·L-1), a—u: 0, 0.1, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5. Inset: the linear fit plot of the 1/(F-F0) as a function of 1/[G] to calculate the complex stability constants. (B) 106c(calcium perchlorate)/(mol·L-1), a—k: 0, 0.2, 0.3, 0.4, 0.5, 0.6, 1.1, 1.6, 2.1, 2.6, 5.6. Inset: the linear fit plot of lg[(F0-F)/F] as a function of lg[G] to calculate the complex stability constants. λex=300 nm.

Fig.4 Fluorescence spectra of crown ether 2(1.0×10-6 mol/L) in the presence of different concentrations of sodium perchlorate(A) and calcium perchlorate(B ) in CH3CN (A) 106c(sodium perchlorate)/(mol·L-1), a—m: 0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0; (B) 106c(calcium perchlorate)/(mol·L-1), a—p: 0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 9.0. Insets: the linear fit plot of the 1/(F-F0) as a function of 1/[G] to calculate the complex stability constants. λex=300 nm.

Fig.5 Fluorescence spectra of crown ether 3(1.0×10-6 mol/L) in the presence of different concentrations of sodium perchlorate in CH3CN(A) and fluorescence spectra of crown ether 4(5.0×10-7 mol/L) in the presence of different concentrations of magnesium perchlorate in CH3CN(B) (A) 106c(sodium perchlorate)/(mol·L-1), a—p: 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60. (B) 103c(magnesium perchlorate)/(mol·L-1), a—j: 0, 2.0, 3.0, 4.0, 5.0, 6.0,6.5,7.0, 8.0. Inset: the linear fit plot of the 1/(F-F0) as a function of 1/[G] to calculate the complex stability constants. λex=300 nm.

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