己基乙二胺-TFS型质子化离子液体与水分子间氢键相互作用的研究

doi:10.11949/0438-1157.20190431

摘要/Abstract

摘要：

通过前期实验研究，己基乙二胺-三氟甲磺酸([HHex][TFS])型质子化离子液体(protic ionic liquid，PIL)的极性部位具有两个氨基，亲水性较强，能够与水混溶90%(质量)(H₂O/ PIL)以上。因此利用密度泛函理论(density functional theory，DFT)，在M06-2X/6-311G(d,p)的水平下，对 [HHex][TFS]与H₂O分子间形成的氢键作用进行了研究。设计了[HHex][TFS]分别与nH₂O (n = 1, 2, 6) 相结合的构型，并得到了较稳定构型共8种(S1~S8)，计算了其分子间的相互作用能(ΔE ₀ ^BSSE)、分子振动频率(Δν)、二阶微扰能、电子密度(ρ _c)以及Laplace值(?² ρ _c)。分析结果显示，[HHex][TFS]与水分子间形成了较强的氢键，[HHex][TFS]与H₂O结合数量增加，构型中氢键相互作用增强，即S4(n=1)＜S6(n=2)＜S8(n=6)。

关键词: 质子化离子液体, 水分子, 氢键作用, 密度泛函理论

Abstract:

The protic ionic liquid (PIL) comprising with hexylethylenediaminium (HHex) cation and trifluoromethane sulfonate (TFS) anion forming [HHex][TFS] is hydrophilic and highly miscible with water ( H₂O /PIL above 90%(mass)) as there are two amines in the polar group. Therefore, in this study, the hydrogen bonding interaction between [HHex][TFS] and water molecules was investigated using the density functional theory (DFT) at M06-2X/6-311G (d,p) level, the configurations of [HHex][TFS]-nH₂O (n= 1, 2, 6) S1-S8 were designed and optimized . The results of molecular interaction (ΔE ₀ ^BSSE), vibration spectra (Δν), the second-order perturbation (E ⁽²⁾), and electron density (ρ _c) and Laplace value (?² ρ _c) show that the hydrogen bonding interaction increase with increasing the water content: S4 (n= 1)＜S6 (n= 2)＜S8 (n= 6).

Key words: protic ionic liquids, H₂O, hydrogen bonding, density functional theory

中图分类号:

O 62

郑勋,徐宇,花儿. 己基乙二胺-TFS型质子化离子液体与水分子间氢键相互作用的研究[J]. 化工学报, 2019, 70(S2): 85-93.

Xun ZHENG,Yu XU,Er HUA. Water and hydrogen bonding study on protic ionic liquids composed of hexylethylenediamine cation and trifluoromethanesulfonate anion[J]. CIESC Journal, 2019, 70(S2): 85-93.

图/表 10

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Structures	ΔE ₀/(kcal·mol^-1)	ΔE ₀ ^BSSE/(kcal·mol^-1)
[HHex][TFS]-H₂O-S1	-16.92	-11.27
[HHex][TFS]-H₂O-S2	-11.70	-9.38
[HHex][TFS]-H₂O-S3	-16.91	-12.19
[HHex][TFS]-H₂O-S4	-23.02	-17.31
[HHex][TFS]-2H₂O-S5	-22.14	-14.82
[HHex][TFS]-2H₂O-S6	-38.77	-31.06
[HHex][TFS]-2H₂O-S7	-27.32	-19.45
[HHex][TFS]-6H₂O-S8	-91.81	-71.71

Structures	ΔE ₀/(kcal·mol^-1)	ΔE ₀ ^BSSE/(kcal·mol^-1)
[HHex][TFS]-H₂O-S1	-16.92	-11.27
[HHex][TFS]-H₂O-S2	-11.70	-9.38
[HHex][TFS]-H₂O-S3	-16.91	-12.19
[HHex][TFS]-H₂O-S4	-23.02	-17.31
[HHex][TFS]-2H₂O-S5	-22.14	-14.82
[HHex][TFS]-2H₂O-S6	-38.77	-31.06
[HHex][TFS]-2H₂O-S7	-27.32	-19.45
[HHex][TFS]-6H₂O-S8	-91.81	-71.71

Structures	N—H bond	ν/cm^-1	Δν/cm^-1	r/nm	Δr/nm
H₂O	1O—2H	3893.61		0.0959
H₂O	1O—3H	3893.61		0.0959
[HHex][TFS]	28N—31H	2389.55		0.1091
	28N—26H	3406.22		0.1027
	28N—25H	3560.49		0.1017
	27N—29H	3536.44		0.1016
[HHex][TFS]-H₂O-S1	28N—31H	2872.39	-482.84	0.1054	-0.0036
[HHex][TFS]-H₂O-S1	28N—26H	2938.01	+468.21	0.1053	0.0026
[HHex][TFS]-H₂O-S2	28N—31H	3498.83	-1109.28	0.1022	-0.0069
[HHex][TFS]-H₂O-S2	28N—25H	3379.68	+180.81	0.1027	0.0010
[HHex][TFS]-H₂O-S3	28N—31H	2873.71	-484.16	0.1054	-0.0037
[HHex][TFS]-H₂O-S3	28N—26H	2937.13	+469.09	0.1053	0.0026
[HHex][TFS]-H₂O-S4	28N—31H	3039.79	-650.24	0.1048	-0.0043
[HHex][TFS]-H₂O-S4	28N—26H	2654.10	+906.39	0.1068	0.0051
[HHex][TFS]-2H₂O-S5	28N—31H	3500.96	-1111.41	0.1022	-0.0069
	28N—25H	3380.25	+180.24	0.1027	0.0010
	43O—45H	3691.90	+201.71	0.0971	0.0012
[HHex][TFS]-2H₂O-S6	28N—31H	3178.23	-788.68	0.1040	-0.0051
	28N—26H	2278.36	+1127.86	0.1094	0.0067
	40O—41H	3520.43	+373.18	0.0980	0.0021
	40O—42H	3554.48	+339.13	0.0980	0.0021
	43O—44H	3820.36	+73.25	0.0965	0.0006
	43O—45H	3820.36	+73.25	0.0967	0.0008
[HHex][TFS]-2H₂O-S7	28N—31H	3101.66	-712.11	0.1044	-0.0046
	28N—25H	3389.28	+171.21	0.1027	0.0010
	40O—42H	3748.55	+145.06	0.0971	0.0012
[HHex][TFS]-6H₂O-S8	28N—31H	3370.45	-980.90	0.1030	-0.0061
	28N—26H	2600.30	+805.92	0.1072	0.0044
	40O—42H	3358.27	+535.34	0.0986	0.0027
	43O—45H	3569.23	+324.38	0.0978	0.0019
	49O—51H	3773.38	+120.23	0.0970	0.0011
	52O—53H	3546.59	+347.02	0.0978	0.0019
	55O—56H	3358.27	+535.34	0.0983	0.0024

Structures	N—H bond	ν/cm^-1	Δν/cm^-1	r/nm	Δr/nm
H₂O	1O—2H	3893.61		0.0959
H₂O	1O—3H	3893.61		0.0959
[HHex][TFS]	28N—31H	2389.55		0.1091
	28N—26H	3406.22		0.1027
	28N—25H	3560.49		0.1017
	27N—29H	3536.44		0.1016
[HHex][TFS]-H₂O-S1	28N—31H	2872.39	-482.84	0.1054	-0.0036
[HHex][TFS]-H₂O-S1	28N—26H	2938.01	+468.21	0.1053	0.0026
[HHex][TFS]-H₂O-S2	28N—31H	3498.83	-1109.28	0.1022	-0.0069
[HHex][TFS]-H₂O-S2	28N—25H	3379.68	+180.81	0.1027	0.0010
[HHex][TFS]-H₂O-S3	28N—31H	2873.71	-484.16	0.1054	-0.0037
[HHex][TFS]-H₂O-S3	28N—26H	2937.13	+469.09	0.1053	0.0026
[HHex][TFS]-H₂O-S4	28N—31H	3039.79	-650.24	0.1048	-0.0043
[HHex][TFS]-H₂O-S4	28N—26H	2654.10	+906.39	0.1068	0.0051
[HHex][TFS]-2H₂O-S5	28N—31H	3500.96	-1111.41	0.1022	-0.0069
	28N—25H	3380.25	+180.24	0.1027	0.0010
	43O—45H	3691.90	+201.71	0.0971	0.0012
[HHex][TFS]-2H₂O-S6	28N—31H	3178.23	-788.68	0.1040	-0.0051
	28N—26H	2278.36	+1127.86	0.1094	0.0067
	40O—41H	3520.43	+373.18	0.0980	0.0021
	40O—42H	3554.48	+339.13	0.0980	0.0021
	43O—44H	3820.36	+73.25	0.0965	0.0006
	43O—45H	3820.36	+73.25	0.0967	0.0008
[HHex][TFS]-2H₂O-S7	28N—31H	3101.66	-712.11	0.1044	-0.0046
	28N—25H	3389.28	+171.21	0.1027	0.0010
	40O—42H	3748.55	+145.06	0.0971	0.0012
[HHex][TFS]-6H₂O-S8	28N—31H	3370.45	-980.90	0.1030	-0.0061
	28N—26H	2600.30	+805.92	0.1072	0.0044
	40O—42H	3358.27	+535.34	0.0986	0.0027
	43O—45H	3569.23	+324.38	0.0978	0.0019
	49O—51H	3773.38	+120.23	0.0970	0.0011
	52O—53H	3546.59	+347.02	0.0978	0.0019
	55O—56H	3358.27	+535.34	0.0983	0.0024

Atom	H₂O	[HHex][TFS]	S1	S2	S3	S4	S5	S6	S7	S8
N27		-0.676	-0.676	-0.684	-0.676	-0.736	-0.709	-0.737	-0.677	-0.738
N28		-0.744	-0.757	-0.754	-0.757	-0.762	-0.749	-0.767	-0.772	-0.751
H29		0.344	0.342	0.342	0.342	0.394	0.355	0.398	0.340	0.412
H30		0.200	0.200	0.199	0.200	0.200	0.199	0.199	0.199	0.199
H31		0.482	0.476	0.439	0.476	0.477	0.441	0.471	0.469	0.475
O34		-0.919	-0.981	-0.928	-0.981	-0.927	-0.926	-0.966	-0.984	-0.999
O35		-1.026	-1.023	-1.035	-1.023	-1.060	-1.037	-1.057	-1.025	-1.048
O39		-1.023	-1.021	-1.021	-1.021	-1.031	-1.019	-1.022	-1.022	-1.023
O40	-0.899		-0.962	-0.934	-0.962	-0.958	-0.935	-0.981	-0.965	-0.988
H41	0.449		0.500	0.478	0.500	0.501	0.478	0.503	0.496	0.504
H42	0.449		0.503	0.478	0.503	0.497	0.479	0.517	0.500	0.514
O43							-0.947	-0.953	-0.932	-0.982
H44							0.451	0.490	0.476	0.476
H45							0.481	0.487	0.477	0.513
O46										-0.954
H47										0.479
H48										0.477
O49										-0.976
H50										0.495
H51										0.494
O52										-0.978
H53										0.506
H54										0.460
O55										-0.986
H56										0.501
H57										0.487