4-(4-羧基苯氧基)间苯二甲酸构筑的过渡金属配位聚合物: 合成、 晶体结构、 荧光传感与光催化

doi:10.7503/cjcu20190493

摘要/Abstract

摘要：

采用水热法合成了4个配位聚合物[Zn(Hcpoia)(2,2'-bpy)·H₂O]_n(1)和[M(Hcpoia)(phen)]_n·nH₂O[M=Zn(2), Mn(3), Co(4); H₃cpoia=4-(4-羧基苯氧基)间苯二甲酸; 2,2'-bpy=2,2'-联吡啶; phen=1,10-邻菲罗啉], 利用X射线单晶衍射分析确定了配合物的晶体结构. 配合物1为一维链状结构, 中心Zn ²⁺离子的配位环境为[ZnO₄N₂]扭曲的八面体构型, 配体Hcpoia ^2-以μ₁∶η ¹η ⁰和μ₁∶η ¹η ¹配位模式桥连相邻的Zn ²⁺离子. 配合物2和4的结构与配合物1类似, 是由配体Hcpoia ^2-以μ₁∶η ¹η ⁰和μ₁∶η ¹η ¹配位模式联接[MO₄N₂]结构单元而形成的一维链状结构. 配合物1, 2和4中均存在分子间氢键(O—H…O), 氢键的存在使一维链连接形成二维超分子结构. 配合物3为二维网状结构, Mn ²⁺离子的配位环境为[MnO₄N₂]扭曲的八面体构型, 配体Hcpoia ^2-以μ₂∶η ¹η ¹配位模式桥连相邻Mn ²⁺离子形成[Mn₂COO₂]结构单元, 该结构单元被Hcpoia ^2-连接形成二维结构. 在4个配合物中, 2,2'-bpy和phen配体均以端基的形式与金属离子螯合配位. 研究了水溶液中抗生素分子和Fe ³⁺离子对配合物1与荧光强度的影响, 实验结果表明, 甲硝唑、 Fe ³⁺离子对配合物1有荧光猝灭作用, 并进一步考察了甲硝唑浓度和Fe ³⁺离子浓度对配合物1荧光强度的影响. 基于荧光猝灭机理, 配合物1可以用作荧光传感器检测水溶液中的甲硝唑和Fe ³⁺离子. 研究了配合物4对罗丹明B(RhB)的催化降解性能, 发现在氙灯照射和H₂O₂存在条件下, 配合物4对RhB具有较好的光催化降解作用.

关键词: 过渡金属配位聚合物, 晶体结构, 荧光, 光催化

Abstract:

Four new transition metal coordination polymers, [Zn(Hcpoia)(2,2'-bpy)·H₂O]_n(1) and [M(Hcpoia)(phen)]_n·nH₂O[M=Zn(2), Mn(3), Co(4); H₃cpoia=4-(4-carboxyphenoxy)isophthalic acid; 2,2'-bpy=2,2'-bipyridine; phen=1,10-phenanthroline], were synthesized by hydrothermal method and characterized by X-ray single crystal diffraction(XRD). Complex 1 features a one-dimensional chain structure, and Zn ²⁺ ions adopt a [ZnO₄N₂] distorted octahedral configuration. Zn ²⁺ ions are linked by Hcpoia ^2- ligands through μ₁∶η ¹η ⁰ and μ₁∶η ¹η ¹ coordination modes. The structures of complexes 2 and 4 are similar to that of complex 1 with one-dimensional chain structure, which is formed by Hcpoia ^2- ligands connecting [MO₄N₂] structural units through μ₁∶η ¹η ⁰/μ₁∶η ¹η ¹ coordination modes. The one-dimensional chains of complexes 1, 2 and 4 are developed into two-dimensional structures by intermolecular hydrogen bonds. Complex 3 has a two-dimensional network structure, in which Mn ²⁺ ions take a [MnO₄N₂] distorted octahedral configuration. Hcpoia ^2- ligands link adjacent Mn ²⁺ ions through μ₁∶η ¹η ⁰ and μ₁∶η ¹η ¹ coordination modes to form [Mn₂COO₂] binuclear units. The binuclear units are connected by Hcpoia ^2- ligands to form a two-dimensional structure. In complexes 1—4, both 2,2'-bpy and phen ligands as terminal groups chelate to metal ions. The effects of antibiotics and Fe ³⁺ ions in aqueous solution on the fluorescence intensity of complex 1 were studied. The results show that metronidazole and Fe ³⁺ ions exert quenching effects on fluorescence of complex 1. The effects of various concentrations of metronidazole and Fe ³⁺ ions on the fluorescence intensity of complex 1 were further studied. Based on the fluorescence quenching mechanism, complex 1 can be used as a fluorescence sensor for detection of metronidazole and Fe ³⁺ ions in aqueous solution. The catalytic performance of complex 4 on RhB was studied. The experimental results show that complex 4 has good photocatalytic degradation of RhB in the presence of hydrogen peroxide and xenon lamp irradiation.

Key words: Transition metal coordination polymer, Crystal Structure, Fluorescence, Photocatalysis

中图分类号:

O614

刘东枚,苏雅静,李姗姗,许奇炜,李夏. 4-(4-羧基苯氧基)间苯二甲酸构筑的过渡金属配位聚合物: 合成、晶体结构、荧光传感与光催化[J]. 高等学校化学学报, 2020, 41(2): 253-261.

LIU Dongmei,SU Yajing,LI Shanshan,XU Qiwei,LI Xia. Transition Metal Coordination Polymers Constructed by 4-(4-Carboxyphenoxy)isophthalic Acid: Synthesis, Crystal Structure, Fluorescence Sensing and Photocatalysis ^†[J]. Chemical Journal of Chinese Universities, 2020, 41(2): 253-261.

图/表 11

Table 1 Crystallographic data of complexes 1—4

Complex	1	2	3	4
Empirical formula	C₂₅H₁₈N₂O₈Zn	C₂₇H₁₈N₂O₈Zn	C₂₇H₁₈MnN₂O₈	C₅₄H₃₆Co₂N₄O₁₆
Formula weight	539.78	563.80	553.37	1114.73
Crystal system	Triclinic	Triclinic	Monoclinic	Triclinic
Space group	P $1 ˉ$	P $1 ˉ$	P2₁/c	P $1 ˉ$
a/nm	0.97529(7)	0.99103(5)	1.42226(4)	0.97396(3)
b/nm	1.01915(5)	1.00828(5)	1.09657(3)	1.00174(3)
c/nm	1.34860(6)	1.40052(6)	1.53718(5)	1.38980(4)
α/(°)	69.525(4)	96.263(2)	90	97.159(2)
β/(°)	89.020(5)	106.8670(10)	96.0640(10)	107.019
γ/(°)	68.440(6)	110.7200(10)	90	107.595
Volume/nm³	1.1583(12)	1.2171(10)	2.3840(12)	1.2017(7)
Z	2	2	4	1
D_calcd/(g·cm^-3)	1.548	1.538	1.542	1.540
F(000)	552.0	576.0	1132.0	570
Crystal size/mm³	0.25×0.23×0.21	0.21×0.25×0.23	0.32×0.25×0.14	0.15×0.1×0.05
2θ range for data collection/(°)	9.832—133.2	4.632—52.744	4.572—55.014	9.526—133.192
Index range	-11≤h≤11,	-11≤h≤11,	-16≤h≤18,	-6≤h≤11
	-12≤k≤11,	-11≤k≤11,	-14≤k≤14,	-12≤k≤11,
	-15≤l≤16	-14≤l≤16	-19≤l≤19	-16≤l≤17
Reflections collected	9868	11800	27932	13362
Independent reflections	3999[R_int=0.0914]	4166[R_int=0.0197]	5473[R_int=0.0480]	4700[R_int=0.0619]
Data/restraints/parameters	3999/0/327	4166/7/345	5473/1/345	4700/0/345
Goodness-of-fit on F²	1.113	1.063	1.084	1.113
Final R indexes[I≥2σ(I)]	R₁=0.0851,	R₁=0.0334,	R₁=0.0619,	R₁=0.0547,
	wR₂=0.2576	wR₂=0.0847	wR₂=0.1583	wR₂=0.1582
Final R indexes(all data)	R₁=0.0952,	R₁=0.0386,	R₁=0.0963,	R₁=0.0560,
	wR₂=0.2929	wR₂=0.0875	wR₂=0.1747	wR₂=0.1593
CCDC No.	1943993	1943994	1943992	1943991

Table 1 Crystallographic data of complexes 1—4

Complex	1	2	3	4
Empirical formula	C₂₅H₁₈N₂O₈Zn	C₂₇H₁₈N₂O₈Zn	C₂₇H₁₈MnN₂O₈	C₅₄H₃₆Co₂N₄O₁₆
Formula weight	539.78	563.80	553.37	1114.73
Crystal system	Triclinic	Triclinic	Monoclinic	Triclinic
Space group	P $1 ˉ$	P $1 ˉ$	P2₁/c	P $1 ˉ$
a/nm	0.97529(7)	0.99103(5)	1.42226(4)	0.97396(3)
b/nm	1.01915(5)	1.00828(5)	1.09657(3)	1.00174(3)
c/nm	1.34860(6)	1.40052(6)	1.53718(5)	1.38980(4)
α/(°)	69.525(4)	96.263(2)	90	97.159(2)
β/(°)	89.020(5)	106.8670(10)	96.0640(10)	107.019
γ/(°)	68.440(6)	110.7200(10)	90	107.595
Volume/nm³	1.1583(12)	1.2171(10)	2.3840(12)	1.2017(7)
Z	2	2	4	1
D_calcd/(g·cm^-3)	1.548	1.538	1.542	1.540
F(000)	552.0	576.0	1132.0	570
Crystal size/mm³	0.25×0.23×0.21	0.21×0.25×0.23	0.32×0.25×0.14	0.15×0.1×0.05
2θ range for data collection/(°)	9.832—133.2	4.632—52.744	4.572—55.014	9.526—133.192
Index range	-11≤h≤11,	-11≤h≤11,	-16≤h≤18,	-6≤h≤11
	-12≤k≤11,	-11≤k≤11,	-14≤k≤14,	-12≤k≤11,
	-15≤l≤16	-14≤l≤16	-19≤l≤19	-16≤l≤17
Reflections collected	9868	11800	27932	13362
Independent reflections	3999[R_int=0.0914]	4166[R_int=0.0197]	5473[R_int=0.0480]	4700[R_int=0.0619]
Data/restraints/parameters	3999/0/327	4166/7/345	5473/1/345	4700/0/345
Goodness-of-fit on F²	1.113	1.063	1.084	1.113
Final R indexes[I≥2σ(I)]	R₁=0.0851,	R₁=0.0334,	R₁=0.0619,	R₁=0.0547,
	wR₂=0.2576	wR₂=0.0847	wR₂=0.1583	wR₂=0.1582
Final R indexes(all data)	R₁=0.0952,	R₁=0.0386,	R₁=0.0963,	R₁=0.0560,
	wR₂=0.2929	wR₂=0.0875	wR₂=0.1747	wR₂=0.1593
CCDC No.	1943993	1943994	1943992	1943991

Fig.1 Coordination environment of Zn(Ⅱ) ions(A), 1D chain structure(B) and 2D structure(C) of complex 1 Symmetry code: A: x, -1+y, z.

Fig.2 Coordination environment of Co(Ⅱ) ions(A), 1D chain structure(B) and 2D structure(C) of complex 4 Symmetry code: A: x, 1+y, z.

Fig.3 Coordination environment of Mn(Ⅱ) ions(A), secondary building unit(B) and 2D structure(C) of complex 3 Symmetry code: A: 1-x, 1-y, -z.

Fig.4 Emission spectra of complex 1 and ligands

Fig.5 Emission spectra(A) and histogram of fluorescence intensity(B) of complex 1 in aqueous solution containing different antibiotics a. Thiamphenicol; b. H2O; c. amoxicillin; d. sulfathiazole; e. sulfadiazine; f. roxithromycin; g. azithromycin; h. penicillin; i. sulfadimidine; j. ornidazole; k. metronidazole.

Fig.6 Emission spectra(A) and histogram of fluorescence intensity(B) of complex 1 in different concentrations of metronidazole solution c(Metronidazole)/(mol·L-1): a. 0; b. 10-6; c. 10-5; d. 10-4; e. 10-3; f. 10-2.

Fig.7 Emission spectra(A) and histogram of fluorescence intensity(B) of complex 1 in solution containing different metal ions a. Pb2+; b. Al3+; c. Cu2+; d. Na+; e. Ba2+; f. Ni2+; g. K+; h. Ag+; i. Mg2+; j. H2O; k. Li2+; l. Cd2+; m. Co2+; n. Ca2+; o. Zn2+; p. Cr3+; q. Fe3+.

Fig.8 Emission spectra(A) and histogram of fluorescence intensity(B) of complex 1 in different concentrations of Fe3+ ions solution. c(Fe3+)/(mol·L-1): a. 0; b. 10-7; c. 10-6; d. 10-5; e. 10-4; f. 10-3; g. 10-2.

Fig.9 Time-dependent UV-Vis absorption spectra for degradation of RhB using complex 4 t/min: a. 0; b. 10; c. 20; d. 30; e. 40; f. 50; g. 60; h. 70; i. 80; j. 90.

Fig.10 Time-dependent UV-Vis absorption spectra for degradation of RhB with H2O2(A), RhB with complex 4+H2O2(B) and the degradation rate of RhB under different conditions(C) (A), (B) t/min: a. 0; b. 10; c. 20; d. 30; e. 40; f. 50; g. 60; h. 70; i. 80; j. 90. (C) a. Complex 4+RhB; b. H2O2+RhB; c. complex 4+H2O2+RhB.

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