Theoretical study on mechanism of silicon heteroatoms to improve the complexation ability of crown ethers to lithium ions

doi:10.11949/0438-1157.20210027

Abstract

Abstract:

Doping Si atoms into crown ethers has the potential to greatly enhance their complexation ability to metal ions, but the regulation mechanism is still unclear. 12-Crown-4, 1,1-demethyl-1-sila-12-crown-4, 1,1,2,2-tetramethyl-1,2-disila-12-crown-4, 1,1,2,2,4,4,5,5-octamethyl-1,2,4,5-tetrasila-12-crown-4 and 1,1,2,2,7,7,8,8-octamethyl-1,2,7,8-tetrasila-12-crown-4 were selected as the models and the interactions between crown ethers and Li⁺ were deeply studied by quantum chemical density functional theory calculations. The results show that due to the increase of the O—Li⁺ coordination bond length, the covalent interactions of the 12-crown-4 with two or four Si atoms are slightly weaker, but the electrostatic interactions and dispersion interactions are stronger, and the Pauli repulsions are smaller, which ultimately lead to the stronger interaction between all the Si hetero12-crown-4 and Li⁺ than 12-crown-4. The above mentioned favorable factors stem from the fact that the electrons of the weakly electronegative Si in the Si—O bond are significantly polarized toward O, which enhances the advantage of O's negative electrostatic potential. Meanwhile, the complexion of Si hetero12-crown-4 with Li⁺ causes the —SiMe₂—SiMe₂— or —CH₂—SiMe₂— units to be away from Li⁺, effectively avoiding the Coulombic repulsion between Si—Li⁺. The crown ether-Li⁺ interaction mechanism revealed in this work will provide theoretical guidance for the future designing and synthesizing of heteroatom crown ethers with efficient extraction capabilities.

Key words: crown ether, lithium-ion, silicon, heteroatom, adsorption, sorbents, computational chemistry

摘要：

将Si引入冠醚有希望大幅度提升其对阳离子的络合能力，但其中的调控机理尚不清晰。基于量子化学密度泛函理论计算，以12-冠-4、1，1-2甲基-1-硅杂12-冠-4、1，1，2，2-4甲基-1，2-2硅杂12-冠-4、1，1，2，2，4，4，5，5-8甲基-1，2，4，5-4硅杂12-冠-4和1，1，2，2，7，7，8，8-8甲基-1，2，7，8-4硅杂12-冠-4络合Li⁺为计算模型，探究了冠醚与Li⁺之间的相互作用机理。结果表明，由于O—Li⁺配位键的键长增加，掺杂Si的数量为2和4的Si杂12-冠-4对Li⁺的共价相互作用略弱，但静电相互作用和色散相互作用更强、Pauli排斥作用更小，最终导致所有Si杂12-冠-4对Li⁺的络合能力都比12-冠-4更强。上述有利因素源于Si—O键中Si的电子显著向O极化，同时，Si杂12-冠-4中—SiMe₂—SiMe₂—和—CH₂—SiMe₂—单元远离Li⁺，有效避免了Si—Li⁺之间的静电排斥。揭示的冠醚-Li⁺相互作用机理将为未来设计与合成杂原子冠醚提供理论指导。

关键词: 冠醚, 锂离子, 硅, 杂原子, 吸附, 吸附剂, 计算化学

CLC Number:

O 641

LIANG-SU Zhuocheng, JI Guoxun, SUN Xinli, WANG Bo, ZHANG Shitong, DAI Xing. Theoretical study on mechanism of silicon heteroatoms to improve the complexation ability of crown ethers to lithium ions[J]. CIESC Journal, 2021, 72(6): 3149-3159.

梁苏卓成, 姬国勋, 孙新利, 王波, 张仕通, 代星. 硅杂原子提升冠醚对锂离子络合能力的机理理论研究[J]. 化工学报, 2021, 72(6): 3149-3159.

Figures/Tables 8

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键	距离/?
键	L	L-Li⁺	L^Si/C	L^Si/C-Li⁺	L^Si	L^Si-Li⁺	L^Si-O	L^Si-O-Li⁺	L^Si-M	L^Si-M-Li⁺
C—C	1.517	1.525	1.519	1.523	1.517	1.520	1.516	1.515	1.521	1.519
C—O	1.404	1.430	1.409	1.429	1.402	1.426	1.404	1.422	1.404	1.425
Si—O	—	—	1.689	1.724	1.694	1.733	1.685	1.726	1.691	1.725
Si—Si	—	—	—	—	2.355	2.371	2.351	2.350	2.355	2.356
Si—C	—	—	1.875	1.863	1.885	1.873	1.885	1.876	1.887	1.875
C—Li⁺	—	2.646	—	2.689	—	2.740	—	2.859	—	2.794
Si—Li⁺	—	—	—	2.930	—	3.075	—	3.176	—	3.217
O₁—Li⁺	—	1.872	—	1.724	—	1.892	—	1.990	—	1.955
O₂—Li⁺	—	1.887	—	1.893	—	1.944	—	1.975	—	1.955
O₃—Li⁺	—	1.872	—	1.909	—	1.944	—	2.037	—	1.955
O₄—Li⁺	—	1.887	—	1.865	—	1.892	—	1.964	—	1.955
O—Li⁺	—	1.880	—	1.848	—	1.918	—	1.991	—	1.955

键	距离/?
键	L	L-Li⁺	L^Si/C	L^Si/C-Li⁺	L^Si	L^Si-Li⁺	L^Si-O	L^Si-O-Li⁺	L^Si-M	L^Si-M-Li⁺
C—C	1.517	1.525	1.519	1.523	1.517	1.520	1.516	1.515	1.521	1.519
C—O	1.404	1.430	1.409	1.429	1.402	1.426	1.404	1.422	1.404	1.425
Si—O	—	—	1.689	1.724	1.694	1.733	1.685	1.726	1.691	1.725
Si—Si	—	—	—	—	2.355	2.371	2.351	2.350	2.355	2.356
Si—C	—	—	1.875	1.863	1.885	1.873	1.885	1.876	1.887	1.875
C—Li⁺	—	2.646	—	2.689	—	2.740	—	2.859	—	2.794
Si—Li⁺	—	—	—	2.930	—	3.075	—	3.176	—	3.217
O₁—Li⁺	—	1.872	—	1.724	—	1.892	—	1.990	—	1.955
O₂—Li⁺	—	1.887	—	1.893	—	1.944	—	1.975	—	1.955
O₃—Li⁺	—	1.872	—	1.909	—	1.944	—	2.037	—	1.955
O₄—Li⁺	—	1.887	—	1.865	—	1.892	—	1.964	—	1.955
O—Li⁺	—	1.880	—	1.848	—	1.918	—	1.991	—	1.955

系统	配位键	ρ/a.u.	?²ρ/a.u.	H/a.u.	\|V\|/G
L-Li⁺	O₁—Li⁺	0.0357	0.2554	0.0120	0.766
	O₂—Li⁺	0.0344	0.2412	0.0112	0.770
	O₃—Li⁺	0.0357	0.2554	0.0120	0.766
	O₄—Li⁺	0.0344	0.2413	0.0112	0.771
L^Si/C-Li⁺	O₁—Li⁺	0.0341	0.2404	0.0111	0.771
	O₂—Li⁺	0.0338	0.2367	0.0110	0.769
	O₃—Li⁺	0.0323	0.2241	0.0103	0.771
	O₄—Li⁺	0.0362	0.2605	0.0123	0.767
L^Si-Li⁺	O₁—Li⁺	0.0332	0.2339	0.0110	0.768
	O₂—Li⁺	0.0294	0.1987	0.0091	0.775
	O₃—Li⁺	0.0293	0.1985	0.0090	0.775
	O₄—Li⁺	0.0332	0.2343	0.0110	0.768
L^Si-O-Li⁺	O₁—Li⁺	0.0254	0.1651	0.0073	0.782
	O₂—Li⁺	0.0265	0.1755	0.0080	0.777
	O₃—Li⁺	0.0228	0.1460	0.0063	0.787
	O₄—Li⁺	0.0271	0.1810	0.0084	0.773
L^Si-M-Li⁺	O₁—Li⁺	0.0278	0.1884	0.0087	0.773
	O₂—Li⁺	0.0278	0.1884	0.0087	0.773
	O₃—Li⁺	0.0278	0.1884	0.0087	0.773
	O₄—Li⁺	0.0278	0.1884	0.0087	0.773

系统	配位键	ρ/a.u.	?²ρ/a.u.	H/a.u.	\|V\|/G
L-Li⁺	O₁—Li⁺	0.0357	0.2554	0.0120	0.766
	O₂—Li⁺	0.0344	0.2412	0.0112	0.770
	O₃—Li⁺	0.0357	0.2554	0.0120	0.766
	O₄—Li⁺	0.0344	0.2413	0.0112	0.771
L^Si/C-Li⁺	O₁—Li⁺	0.0341	0.2404	0.0111	0.771
	O₂—Li⁺	0.0338	0.2367	0.0110	0.769
	O₃—Li⁺	0.0323	0.2241	0.0103	0.771
	O₄—Li⁺	0.0362	0.2605	0.0123	0.767
L^Si-Li⁺	O₁—Li⁺	0.0332	0.2339	0.0110	0.768
	O₂—Li⁺	0.0294	0.1987	0.0091	0.775
	O₃—Li⁺	0.0293	0.1985	0.0090	0.775
	O₄—Li⁺	0.0332	0.2343	0.0110	0.768
L^Si-O-Li⁺	O₁—Li⁺	0.0254	0.1651	0.0073	0.782
	O₂—Li⁺	0.0265	0.1755	0.0080	0.777
	O₃—Li⁺	0.0228	0.1460	0.0063	0.787
	O₄—Li⁺	0.0271	0.1810	0.0084	0.773
L^Si-M-Li⁺	O₁—Li⁺	0.0278	0.1884	0.0087	0.773
	O₂—Li⁺	0.0278	0.1884	0.0087	0.773
	O₃—Li⁺	0.0278	0.1884	0.0087	0.773
	O₄—Li⁺	0.0278	0.1884	0.0087	0.773

计算级别		能量/（kcal/mol）	系统
泛函	基组	能量/（kcal/mol）	L-Li⁺	L^Si/C-Li⁺	L^Si-Li⁺	L^Si-O-Li⁺	L^Si-M-Li⁺
B3LYP-D3(BJ)	Def2QZVP	ΔE^int	-104.83	-112.26	-118.53	-124.46	-129.12
B3LYP-D3(BJ)	Def2QZVP	ΔE^geom	11.26	16.72	19.28	23.73	23.57
BLYP-D3(BJ)	QZ4P	ΔE^int(Total)	-102.17	-109.60	-116.03	-122.20	-126.68
		ΔE^els	-73.37	-77.68	-79.59	-77.67	-84.22
		ΔE^orb	-60.55	-61.38	-60.54	-58.37	-59.74
		ΔE^Pauli	40.23	38.70	33.76	24.42	27.83
		ΔE^disp	-8.49	-9.23	-9.65	-10.58	-10.55
B3LYP-D3(BJ)	TZP	ΔE^int(Total)	-105.94	-113.28	-119.41	-125.19	-129.74
		ΔE^els	-76.08	-80.92	-82.34	-81.64	-86.80
		ΔE^orb	-62.55	-63.06	-62.68	-59.28	-62.04
		ΔE^Pauli	39.73	38.38	33.68	24.65	27.98
		ΔE^disp	-7.03	-7.69	-8.07	-8.91	-8.88