硫杂杯芳烃-金属离子的新型配位化合物

doi:10.16085/j.issn.1000-6613.2019-0461

摘要/Abstract

摘要：

选择性分离贵金属、放射金属、碱金属等金属离子是重要研究方向之一。硫杂杯芳烃是一类由硫原子桥链苯酚单元构成的大环化合物。作为第三代超分子材料，硫杂杯芳烃反应位点丰富，上边缘、下边缘以及桥链的硫原子上都有进行功能化的可能性，而功能化后硫杂杯芳烃能够表现出与金属离子优异的配位性能，从而达到选择性分离金属离子的目的。本文介绍了硫杂杯芳烃的合成历史、自身结构特点以及配位机理。在此基础上分析了在硫杂杯芳烃的上缘、下缘引入酯基、酰胺、亚胺/胺等官能团后与碱金属、碱土金属、放射金属、贵金属离子等的配位情况，总结了硫杂杯芳烃自身构型、杯环的大小、溶剂类型等对其配位性能的影响，并深入分析了与金属离子的不同配位机理。本文可以为开发高效选择性分离提取各种金属离子的技术提供理论依据。

关键词: 硫杂杯芳烃, 配位机理, 配合物, 溶剂, 选择性

Abstract:

Selective separation of metal ions such as precious metals, radioactive metals and alkali metals is an important direction of research and development. Thiacalixarene is a class of macrocyclic compounds composed of sulfur atom bridged phenol units. As a third-generation supramolecular material, thiacalixarene has abundant reaction sites, and the upper and lower edges, as well as sulfur atoms of the bridge chain are possibly to be functionalized. The functionalized thiacalixarene can exhibit excellent coordination performance with metal ions, thereby achieving the purpose of selective separation of metal ions. This paper reviewed the synthesis history, structure characteristics and coordination mechanisms of thiacalixarene. Based on this, the coordination of the functional groups such as ester groups, amides and imines/amines on the upper and lower edges of the thiacalixarene with alkali metals, alkaline earth metals, radioactive metals, precious metal ions, etc. was analyzed. The effects of the thiacalixarene structure, the size of the calix ring and the type of solvent on its coordination performance were summarized, and the coordination mechanisms with different metal ions were analyzed in depth. This paper aimed to provide theoretical basis for the development of selective separation technologies for efficient extraction of various metals.

Key words: thiacalixarene, coordination mechanism, coordination complex, solvent, selective

中图分类号:

程衔锟, 熊延杭, 侯雪, 赵卓, 徐亮, 田勇攀. 硫杂杯芳烃-金属离子的新型配位化合物[J]. 化工进展, 2021, 40(1): 259-272.

Xiankun CHENG, Yanhang XIONG, Xue HOU, Zhuo ZHAO, Liang XU, Yongpan TIAN. Thiacalixarene-novel coordination compounds for metal ions[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 259-272.

图/表 27

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硫杂杯芳烃	构象	阳离子	n	lg K_ex
23	锥形	Li(Ⅰ)	0.78±0.01	3.23±0.04
		Na(Ⅰ)	0.92±0.02	4.03±0.06
		K(Ⅰ)	0.80±0.07	3.05±0.19
		Cs(Ⅰ)	—	—
		Ag(Ⅰ)	0.73±0.03	4.20±0.10
	部分锥型	Li(Ⅰ)	0.62±0.01	1.97±0.02
		Na(Ⅰ)	0.82±0.01	3.53±0.04
		K(Ⅰ)	0.65±0.02	3.35±0.05
		Cs(Ⅰ)	0.73±0.01	2.45±0.02
		Ag(Ⅰ)	1.56±0.06	8.37±0.23
	1,3-交替型	Li(Ⅰ)	0.64±0.03	1.99±0.06
		Na(Ⅰ)	1.22±0.03	5.74±0.10
		K(Ⅰ)	2.14±0.12	9.47±0.47
		Cs(Ⅰ)	1.35±0.18	6.28±0.18
		Ag(Ⅰ)	2.01±0.11	9.93±0.42
24	锥形	Li(Ⅰ)	1.91±0.13	8.43±0.52
		Na(Ⅰ)	1.79±0.10	8.03±0.41
		K(Ⅰ)	1.15±0.03	5.43±0.10
		Cs(Ⅰ)	0.62±0.01	2.27±0.04
		Ag(Ⅰ)	1.06±0.12	6.08±0.49
	部分锥型	Li(Ⅰ)	0.98±0.03	4.51±0.08
		Na(Ⅰ)	1.36±0.02	6.44±0.09
		K(Ⅰ)	1.57±0.07	7.32±0.28
		Cs(Ⅰ)	0.91±0.01	3.95±0.04
		Ag(Ⅰ)	1.57±0.13	8.18±0.55
	1,3-交替型	Li(Ⅰ)	0.80±0.03	3.28±0.09
		Na(Ⅰ)	1.87±0.12	8.33±0.46
		K(Ⅰ)	1.99±0.16	9.06±0.63
		Cs(Ⅰ)	1.93±0.14	8.52±0.53
		Ag(Ⅰ)	1.87±0.22	9.83±0.92
25	锥形	Fe(Ⅲ)	0.48±0.02	4.99±0.06
25		Ni(Ⅱ)	1.12±0.08	8.05±0.31
		Ni(Ⅱ)	1.12±0.08	8.05±0.31
		Al(Ⅲ)	1.61±0.10	7.17±0.21
		Al(Ⅲ)	1.61±0.10	7.17±0.21
		Pb(Ⅱ)	1.56±0.12	8.44±0.04
		Pb(Ⅱ)	1.56±0.12	8.44±0.04
		Cd(Ⅱ)	1.88±0.08	10.90±0.33
		Cd(Ⅱ)	1.88±0.08	10.90±0.33
		Co(Ⅱ)	1.88±0.10	10.73±0.36
		Co(Ⅱ)	1.88±0.10	10.73±0.36
		Cu(Ⅱ)	2.30±0.28	13.36±1.17
		Cu(Ⅱ)	2.30±0.28	13.36±1.17
		Ag(Ⅰ)	1.99±0.15	10.01±0.60
		Ag(Ⅰ)	1.99±0.15	10.01±0.60
	部分锥型	Al(Ⅲ)	0.93±0.05	4.91±0.11
	部分锥型	Al(Ⅲ)	0.93±0.05	4.91±0.11
		Fe(Ⅲ)	0.81±0.05	5.13±0.11
		Fe(Ⅲ)	0.81±0.05	5.13±0.11
		Ag(Ⅰ)	1.11±0.04	6.06±0.15
		Ag(Ⅰ)	1.11±0.04	6.06±0.15
		Ni(Ⅱ)	1.15±0.08	7.09±0.23
		Ni(Ⅱ)	1.15±0.08	7.09±0.23
		Cu(Ⅱ)	1.23±0.11	7.48±0.37
		Cu(Ⅱ)	1.23±0.11	7.48±0.37
		Pb(Ⅱ)	1.17±0.07	5.94±0.17
		Pb(Ⅱ)	1.17±0.07	5.94±0.17
	1,3-交替型	Cu(Ⅱ)	0.42±0.03	3.68±0.08
	1,3-交替型	Cu(Ⅱ)	0.42±0.03	3.68±0.08
		Ag(Ⅰ)	1.22±0.06	5.78±0.21
		Ag(Ⅰ)	1.22±0.06	5.78±0.21
		Fe(Ⅲ)	0.43±0.14	3.82±0.29

硫杂杯芳烃	构象	阳离子	n	lg K_ex
23	锥形	Li(Ⅰ)	0.78±0.01	3.23±0.04
		Na(Ⅰ)	0.92±0.02	4.03±0.06
		K(Ⅰ)	0.80±0.07	3.05±0.19
		Cs(Ⅰ)	—	—
		Ag(Ⅰ)	0.73±0.03	4.20±0.10
	部分锥型	Li(Ⅰ)	0.62±0.01	1.97±0.02
		Na(Ⅰ)	0.82±0.01	3.53±0.04
		K(Ⅰ)	0.65±0.02	3.35±0.05
		Cs(Ⅰ)	0.73±0.01	2.45±0.02
		Ag(Ⅰ)	1.56±0.06	8.37±0.23
	1,3-交替型	Li(Ⅰ)	0.64±0.03	1.99±0.06
		Na(Ⅰ)	1.22±0.03	5.74±0.10
		K(Ⅰ)	2.14±0.12	9.47±0.47
		Cs(Ⅰ)	1.35±0.18	6.28±0.18
		Ag(Ⅰ)	2.01±0.11	9.93±0.42
24	锥形	Li(Ⅰ)	1.91±0.13	8.43±0.52
		Na(Ⅰ)	1.79±0.10	8.03±0.41
		K(Ⅰ)	1.15±0.03	5.43±0.10
		Cs(Ⅰ)	0.62±0.01	2.27±0.04
		Ag(Ⅰ)	1.06±0.12	6.08±0.49
	部分锥型	Li(Ⅰ)	0.98±0.03	4.51±0.08
		Na(Ⅰ)	1.36±0.02	6.44±0.09
		K(Ⅰ)	1.57±0.07	7.32±0.28
		Cs(Ⅰ)	0.91±0.01	3.95±0.04
		Ag(Ⅰ)	1.57±0.13	8.18±0.55
	1,3-交替型	Li(Ⅰ)	0.80±0.03	3.28±0.09
		Na(Ⅰ)	1.87±0.12	8.33±0.46
		K(Ⅰ)	1.99±0.16	9.06±0.63
		Cs(Ⅰ)	1.93±0.14	8.52±0.53
		Ag(Ⅰ)	1.87±0.22	9.83±0.92
25	锥形	Fe(Ⅲ)	0.48±0.02	4.99±0.06
25		Ni(Ⅱ)	1.12±0.08	8.05±0.31
		Ni(Ⅱ)	1.12±0.08	8.05±0.31
		Al(Ⅲ)	1.61±0.10	7.17±0.21
		Al(Ⅲ)	1.61±0.10	7.17±0.21
		Pb(Ⅱ)	1.56±0.12	8.44±0.04
		Pb(Ⅱ)	1.56±0.12	8.44±0.04
		Cd(Ⅱ)	1.88±0.08	10.90±0.33
		Cd(Ⅱ)	1.88±0.08	10.90±0.33
		Co(Ⅱ)	1.88±0.10	10.73±0.36
		Co(Ⅱ)	1.88±0.10	10.73±0.36
		Cu(Ⅱ)	2.30±0.28	13.36±1.17
		Cu(Ⅱ)	2.30±0.28	13.36±1.17
		Ag(Ⅰ)	1.99±0.15	10.01±0.60
		Ag(Ⅰ)	1.99±0.15	10.01±0.60
	部分锥型	Al(Ⅲ)	0.93±0.05	4.91±0.11
	部分锥型	Al(Ⅲ)	0.93±0.05	4.91±0.11
		Fe(Ⅲ)	0.81±0.05	5.13±0.11
		Fe(Ⅲ)	0.81±0.05	5.13±0.11
		Ag(Ⅰ)	1.11±0.04	6.06±0.15
		Ag(Ⅰ)	1.11±0.04	6.06±0.15
		Ni(Ⅱ)	1.15±0.08	7.09±0.23
		Ni(Ⅱ)	1.15±0.08	7.09±0.23
		Cu(Ⅱ)	1.23±0.11	7.48±0.37
		Cu(Ⅱ)	1.23±0.11	7.48±0.37
		Pb(Ⅱ)	1.17±0.07	5.94±0.17
		Pb(Ⅱ)	1.17±0.07	5.94±0.17
	1,3-交替型	Cu(Ⅱ)	0.42±0.03	3.68±0.08
	1,3-交替型	Cu(Ⅱ)	0.42±0.03	3.68±0.08
		Ag(Ⅰ)	1.22±0.06	5.78±0.21
		Ag(Ⅰ)	1.22±0.06	5.78±0.21
		Fe(Ⅲ)	0.43±0.14	3.82±0.29

萃取剂	C_Pd(aq)/mmol?L^-1	C_Pd(org)/mmol?L^-1	D_pd	R/%
47	0.24	0.24	>25	>96
48	0.24	0.24	>25	>96
49	0.24	0.05	0.25	20
50	0.25	0.028	0.12	11

萃取剂	C_Pd(aq)/mmol?L^-1	C_Pd(org)/mmol?L^-1	D_pd	R/%
47	0.24	0.24	>25	>96
48	0.24	0.24	>25	>96
49	0.24	0.05	0.25	20
50	0.25	0.028	0.12	11

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