异辛基乙二胺-酰基丙氨酸型质子化离子液体的分子间氢键相互作用

doi:10.11949/0438-1157.20191380

化工学报 ›› 2020, Vol. 71 ›› Issue (S1): 15-22.DOI: 10.11949/0438-1157.20191380

异辛基乙二胺-酰基丙氨酸型质子化离子液体的分子间氢键相互作用

刘佳鑫¹(),徐宇¹,花儿^1,^2,³()

^1.北方民族大学化学与化学工程学院，宁夏银川 750021
^2.北方民族大学国家民委化工技术基础重点实验室，宁夏银川 750021
^3.北方民族大学宁夏太阳能化学转化技术重点实验室，宁夏银川 750021

收稿日期:2019-11-13 修回日期:2019-12-19 出版日期:2020-04-25 发布日期:2020-04-25
通讯作者: 花儿
作者简介:刘佳鑫（1995—），女，硕士研究生，937979876@qq.com
基金资助:
北方民族大学科技创新类重点科研项目(2019 KJ13)

Structure and hydrogen bonding study on acylamino acid protic ionic liquids composed of 2-N-ethylhexylethylenediaminim cation with acylalanineate anions

Jiaxin LIU¹(),Yu XU¹,Er HUA^1,^2,³()

^1.College of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, Ningxia, China
^2.Key Laboratory of Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University, Yinchuan 750021, Ningxia, China
^3.Ningxia Key Laboratory of Solar Chemical Conversion Technology, North Minzu University, Yinchuan 750021, Ningxia, China

Received:2019-11-13 Revised:2019-12-19 Online:2020-04-25 Published:2020-04-25
Contact: Er HUA

摘要/Abstract

摘要：

利用密度泛函理论M06-2X/6-311G(d,p)方法及基组条件下，对异辛基乙二胺-酰基丙氨酸型质子化离子液体[HEtHex]⁺[Acylala]^-(Acyl =butanoyl, hexanoyl)的几何构型进行了优化，分别得到了5种较稳定构型S1~S5。结果显示，[HEtHex][Butlala]及[HEtHex][Hexlala]的基组重叠误差校正后的分子间相互作用能(ΔE₀^BSSE)均在-136.14~-117.26 kcal·mol^-1（1 kcal·mol^-1=4.182 kJ·mol^-1）范围内，其中伯胺质子化构型(S1~S3)的相互作用能(-136.14~-127.01 kcal·mol^-1)大于仲胺质子化构型(S4~S5)(-119.03~-117.26 kcal·mol^-1)。由于[HEtHex][Acylala]阴阳离子间发生了质子转移而形成了较强的O—H…N型氢键，引起[HEtHex]⁺中N—H振动频率消失，并在2400~2815 cm^-1处出现了较强的O—H的伸缩振动，即以分子与分子间的作用力键合。自然键轨道及分子中原子理论计算结果显示，[HEtHex][Acylala]间所形成氢键的稳定化能主要来源于[EtHex]分子中胺基N原子的孤对电子lp(N)与[Acylala]分子中羧基的反键轨道σ*(O—H)间的相互作用。并且分子间氢键能及二阶微扰能分别在18.69 ~ 24.19 kcal·mol^-1及43.58 ~57.58 kcal?mol^-1范围内，属于较强类型氢键作用。

关键词: 酰基氨基酸离子液体, 密度泛函理论, 质子转移, 分子间氢键作用

Abstract:

The possible molecular structures S1—S5 of acylamino acid protic ionic liquids (AA-PILs) composed of 2-N-ethylhexylethylenediaminium cation coupled with acylalanineate anions forming [HEtHex][Acylala] were studied by the density functional theory at M06-2X/6-311G (d,p) level. The obtained BSSE-corrected interaction energies (ΔE₀^BSSE) for all the structures are in the region of -136.14~-117.26 kcal?mol^-1. For each PIL, the values of ΔE₀^BSSE in the [HEtHex]1⁺[Acylala]^-(S1—S3, protonated at the primary amine, -136.14—-127.01 kcal·mol^-1) are larger than in the [HEtHex]2⁺[Acylala]^- structures (S4 and S5, protonated at the secondary amine, -119.03—-117.26 kcal·mol^-1). The IR results show that N—H vibration spectra is disappeared. In the meantime, the stronger O—H vibration spectra appeared in the region of 2400—2815 cm^-1since stronger O—H…N hydrogen bond was formed between [HEtHex] molecule and [Acylala] molecule. The results of natural bond orbital the stabilization energy mainly caused by the interaction between the lone pair electron lp(N) in the [EtHex] and the anti-bonding orbital σ*(O—H) in the [Acylala]: lp(N)→σ*(O—H). The hydrogen bonding energy and the second-order interaction energies are in the range of 18.69—24.19 kcal·mol^-1 and 43.58—57.58 kcal?mol^-1, respectively. H-bonding between [HEtHex] and [Acylala] is classified as the strong hydrogen bond.

Key words: acylamino acid protic ionic liquids, density functional theory, proton transfer, inter molecular hydrogen bonding

中图分类号:

O 641

刘佳鑫, 徐宇, 花儿. 异辛基乙二胺-酰基丙氨酸型质子化离子液体的分子间氢键相互作用[J]. 化工学报, 2020, 71(S1): 15-22.

Jiaxin LIU, Yu XU, Er HUA. Structure and hydrogen bonding study on acylamino acid protic ionic liquids composed of 2-N-ethylhexylethylenediaminim cation with acylalanineate anions[J]. CIESC Journal, 2020, 71(S1): 15-22.

图/表 9

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Structure	N—H bond	r/?	Δr/?
[HEtHex]1⁺	N31—H33	1.0238
	N31—H32	1.0245
[HEtHex]2⁺	N34—H35	1.0252
[HEtHex][Butala]S1	N31—H33	1.6519	0.6281
[HEtHex][Butala]S2	N31—H33	1.6302	0.6064
[HEtHex][Butala]S3	N31—H32	1.6513	0.6268
[HEtHex][Butala]S4	N34—H35	1.5928	0.5676
[HEtHex][Butala]S5	N34—H35	1.5743	0.5491
[HEtHex][Hexala]S1	N31—H33	1.6528	0.6290
[HEtHex][Hexala]S2	N31—H33	1.6304	0.6066
[HEtHex][Hexala]S3	N31—H32	1.6508	0.6263
[HEtHex][Hexala]S4	N34—H35	1.6107	0.5855
[HEtHex][Hexala]S5	N34—H35	1.5775	0.5523

Structure	N—H bond	r/?	Δr/?
[HEtHex]1⁺	N31—H33	1.0238
	N31—H32	1.0245
[HEtHex]2⁺	N34—H35	1.0252
[HEtHex][Butala]S1	N31—H33	1.6519	0.6281
[HEtHex][Butala]S2	N31—H33	1.6302	0.6064
[HEtHex][Butala]S3	N31—H32	1.6513	0.6268
[HEtHex][Butala]S4	N34—H35	1.5928	0.5676
[HEtHex][Butala]S5	N34—H35	1.5743	0.5491
[HEtHex][Hexala]S1	N31—H33	1.6528	0.6290
[HEtHex][Hexala]S2	N31—H33	1.6304	0.6066
[HEtHex][Hexala]S3	N31—H32	1.6508	0.6263
[HEtHex][Hexala]S4	N34—H35	1.6107	0.5855
[HEtHex][Hexala]S5	N34—H35	1.5775	0.5523

Structure	?E₀/(kcal?mol^-1)	?E₀^BSSE/(kcal?mol^-1)	Structure	?E₀/(kcal?mol^-1)	?E₀^BSSE/(kcal?mol^-1)
[HEtHex][Butala]S1	-133.38	-128.68	[HEtHex][Hexala]S1	-133.31	-128.63
[HEtHex][Butala]S2	-132.05	-127.33	[HEtHex][Hexala]S2	-131.97	-127.25
[HEtHex][Butala]S3	-142.15	-136.14	[HEtHex][Hexala]S3	-133.11	-127.01
[HEtHex][Butala]S4	-123.78	-117.26	[HEtHex][Hexala]S4	-125.43	-119.03
[HEtHex][Butala]S5	-124.15	-117.66	[HEtHex][Hexala]S5	-124.11	-117.57

Structure	?E₀/(kcal?mol^-1)	?E₀^BSSE/(kcal?mol^-1)	Structure	?E₀/(kcal?mol^-1)	?E₀^BSSE/(kcal?mol^-1)
[HEtHex][Butala]S1	-133.38	-128.68	[HEtHex][Hexala]S1	-133.31	-128.63
[HEtHex][Butala]S2	-132.05	-127.33	[HEtHex][Hexala]S2	-131.97	-127.25
[HEtHex][Butala]S3	-142.15	-136.14	[HEtHex][Hexala]S3	-133.11	-127.01
[HEtHex][Butala]S4	-123.78	-117.26	[HEtHex][Hexala]S4	-125.43	-119.03
[HEtHex][Butala]S5	-124.15	-117.66	[HEtHex][Hexala]S5	-124.11	-117.57

Structure	O—H bond	ν/cm^-1	Δν/cm^-1
[Butala]	O—H	3832.81
[Hexala]	O—H	3832.02
[HEtHex][Butala]S1	O57—H33	2812.78	1020.03
[HEtHex][Butala]S2	O58—H33	2715.63	1117.18
[HEtHex][Butala]S3	O58—H32	2679.84	1152.97
[HEtHex][Butala]S4	O58—H35	2472.57	1360.24
[HEtHex][Butala]S5	O58—H35	2401.35	1431.46
[HEtHex][Hexala]S1	O57—H33	2813.06	1018.96
[HEtHex][Hexala]S2	O58—H33	2712.18	1119.84
[HEtHex][Hexala]S3	O58—H32	2686.96	1145.06
[HEtHex][Hexala]S4	O57—H35	2565.97	1266.05
[HEtHex][Hexala]S5	O58—H35	2410.52	1421.50

异辛基乙二胺-酰基丙氨酸型质子化离子液体的分子间氢键相互作用

Structure and hydrogen bonding study on acylamino acid protic ionic liquids composed of 2-N-ethylhexylethylenediaminim cation with acylalanineate anions

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Bond	N31	N34	H32	H33	H35	O57	O58	O59
[Butala]^-						-0.780	-0.816	-0.707
[Hexala]^-						-0.780	-0.816	-0.707
[HEtHex]1⁺	-0.690	-0.689	0.437	0.444	0.358
[HEtHex]2⁺	-0.827	-0.554	0.364	0.364	0.424
[HEtHex][Butala]S1	-0.873	-0.687	0.365	0.514	0.341	-0.734	-0.681	-0.66
[HEtHex][Butala]S2	-0.871	-0.689	0.381	0.517	0.344	-0.664	-0.76	-0.659
[HEtHex][Butala]S3	-0.869	-0.691	0.517	0.372	0.365	-0.668	-0.767	-0.66
[HEtHex][Butala]S4	-0.834	-0.719	0.34	0.34	0.513	-0.668	-0.774	-0.659
[HEtHex][Butala]S5	-0.834	-0.708	0.344	0.34	0.512	-0.663	-0.777	-0.659
[HEtHex][Hexala]S1	-0.873	-0.687	0.365	0.514	0.341	-0.681	-0.734	-0.66
[HEtHex][Hexala]S2	-0.871	-0.689	0.381	0.517	0.344	-0.664	-0.76	-0.659
[HEtHex][Hexala]S3	-0.869	-0.692	0.517	0.372	0.368	-0.671	-0.765	-0.658
[HEtHex][Hexala]S4	-0.834	-0.719	0.341	0.34	0.511	-0.746	-0.688	-0.661
[HEtHex][Hexala]S5	-0.834	-0.708	0.344	0.34	0.512	-0.664	-0.776	-0.659

Structure	Charge transfer	E⁽²⁾	Structure	Charge transfer	E⁽²⁾
[HEtHex][Butala]S1	LP(N31)→σ*(H33-O57)	43.67	[HEtHex][Hexala]S1	LP(N31)→σ*(H33-O57)	43.58
[HEtHex][Butala]S2	LP(N31)→σ*(H33-O58)	47.74	[HEtHex][Hexala]S2	LP(N31)→σ*(H33-O58)	47.72
[HEtHex][Butala]S3	LP(N31)→σ*(H32-O58)	47.33	[HEtHex][Hexala]S3	LP(N31)→σ*(H32-O58)	47.48
[HEtHex][Butala]S4	LP(N34)→σ*(H35-O58)	54.49	[HEtHex][Hexala]S4	LP(N34)→σ*(H35-O57)	50.85
[HEtHex][Butala]S5	LP(N34)→σ*(H35-O58)	57.58	[HEtHex][Hexala]S5	LP(N34)→σ*(H35-O58)	56.86

Structure	BCP	ρ_c/a.u.	?²ρ_c/a.u.	G(r)/a.u.	V(r)/a.u.	H(r)/a.u.	E_HB/(kcal?mol^-1)
[HEtHex][Butala]S1	N31…H33—O57	0.061	0.101	0.043	-0.06	-0.017	18.76
[HEtHex][Butala]S2	N31…H33—O58	0.065	0.098	0.044	-0.064	-0.02	20.06
[HEtHex][Butala]S3	N31…H32—O58	0.062	0.095	0.042	-0.06	-0.018	18.69
[HEtHex][Butala]S4	N34…H35—O58	0.073	0.086	0.047	-0.073	-0.026	22.87
[HEtHex][Butala]S5	N34…H35—O58	0.076	0.083	0.049	-0.077	-0.028	24.19
[HEtHex][Hexala]S1	N31…H33—O57	0.061	0.101	0.042	-0.06	-0.017	18.72
[HEtHex][Hexala]S2	N31…H33—O58	0.065	0.098	0.044	-0.064	-0.02	20.06
[HEtHex][Hexala]S3	N31…H32—O58	0.062	0.095	0.042	-0.06	-0.018	18.74
[HEtHex][Hexala]S4	N34…H35—O57	0.070	0.090	0.046	-0.069	-0.023	21.70
[HEtHex][Hexala]S5	N34…H35—O58	0.076	0.083	0.049	-0.076	-0.028	23.95

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