柱芳烃与烷烃间C―H…π和C―H…O的作用本质及协同性

doi:10.7503/cjcu20200291

摘要/Abstract

摘要：

以CCSD(T)/CBS方法的结合能计算结果为标准, 选择CAM-B3LYP-D3BJ/def2-SVPD密度泛函理论方法计算了甲氧基柱[5]芳烃(MeP5)与C_nH₂_n₊₂(n=1~10, 12, 14, 16) 复合物的结合能, 结果表明, 它们之间存在强烈的相互作用, 且随着烷烃分子碳链的增长而增大; 热力学函数计算结果表明, 在298.15 K, 101325 Pa下, MeP5与C_nH₂_n₊₂(n=3~10, 12, 14, 16)形成复合物的过程中, ΔG和ΔH均小于零, 是焓驱动的自发过程. 烷烃与MeP5之间C―H…π和C―H…O的协同作用是主客体复合物稳定化的起因, 用二代绝对局域分子轨道能量分解(ALMO-EDA)方法分析此协同作用, 发现其中静电作用和色散作用的贡献相近, 二者加和约占总吸引的94%, 极化能和电荷转移能仅占6%.

关键词: 柱[5]芳烃, 烷烃, C―H…π, C―H…O, 协同作用本质

Abstract:

Using the calculation result of the binding energy of the CCSD(T)/CBS method as the standard, the CAM-B3LYP-D3BJ/def2-SVPD density functional theory(DFT) method was chosed to calculate the bin- ding energy of the MeP5…C_nH₂_n₊₂(n=1—10, 12, 14, 16) complexes. The results show that there is a strong interaction between the host and guest, and the binding energy increases with the growth of the alkane carbon chain. The Gibbs free energy and enthalpy change are both less than zero at standard conditions(nominally 298.15 K, 101325 Pa), which indicating that the formation of the complexes is spontaneous, and the main driving force associated with is enthalpy. The nature and cooperation of the C―H…π and C―H…O interactions between alkanes and dimethoxypillar[5]arene(MeP5) were explored using the absolutely localized molecular orbitals energy decomposition analysis(ALMO-EDA) method, and found that the sum of the electrostatic and dispersion effects accounts for about 94% of the total attraction, and their contribution is similar, with polarization and charge transfer accounting for only 6%.

Key words: Pillar[5]arene, Alkanes, C―H…π, C―H…O, Nature of cooperative interaction

中图分类号:

O641.3

TrendMD:

孙涛, 王一波. 柱芳烃与烷烃间C―H…π和C―H…O的作用本质及协同性. 高等学校化学学报, 2020, 41(9): 2046.

SUN Tao, WANG Yibo. Theoretical Study on the Nature and Cooperation of C―H•••O and C―H•••π Interactions in the Pillar[5]arene and n⁃Alkanes Complexes. Chem. J. Chinese Universities, 2020, 41(9): 2046.

图/表 12

Fig.1 Top(A) and side(B) view of C10H14O2…C8H18

Table 1 Binding energies(ΔEb) of C10H14O2…C8H18 complex using density functional theory methods with different basis sets

Method	ΔE_b/(kJ·mol^-1)		Method	ΔE_b/(kJ·mol^-1)
Method	def2?SVPD	def2?TZVPP	Method	def2?SVPD	def2?TZVPP
CCSD(T)/CBS	-23.77	-23.77	PBE0?D3BJ	-24.69	-24.89
ωB97X?V	-24.31	-24.81	B3LYP?D3BJ	-25.10	-25.31
ωB97M?V	-24.48	-25.19	B3PW91?D3BJ	-24.85	-25.15
ωB97X?D	-28.03	-28.58	CAM?B3LYP?D3BJ	-23.97	-24.14
M06?2X?D3	-23.26	-23.10	LC?ωPBE?D3BJ	-24.56	-24.77
PBE?D3BJ	-24.94	-25.15	B2PLYP?D3BJ	-21.55	-21.92

Fig.2 Top(A) and side(B) views of optimized geometries of MeP5

Fig.3 Top(A) and side(B) views of optimized geometries of MeP5…C4H10

Table 2 Binding energies of MeP5…CnH2n+2(n=1―10, 12, 14, 16)

Complex	$? E B 3 P W 91 - D 3 B J C P$ / (kJ·mol^-1)	$? E C A M - B 3 L Y P - D 3 B J C P$ / (kJ·mol^-1)	Complex	$? E B 3 P W 91 - D 3 B J C P$ / (kJ·mol^-1)	$? E C A M - B 3 L Y P - D 3 B J C P$ / (kJ·mol^-1)
MeP5…CH₄	-32.68	-30.33	MeP5…C₈H₁₈	-129.37	-113.80
MeP5…C₂H₆	-55.69	-49.62	MeP5 …C₉H₂₀	-133.43	-117.53
MeP5 …C₃H₈	-74.35	-65.73	MeP5…C₁₀H₂₂	-137.74	-121.38
MeP5…C₄H₁₀	-91.42	-81.34	MeP5…C₁₂H₂₆	-141.92	-124.77
MeP5…C₅H₁₂	-103.85	-91.17	MeP5…C₁₄H₃₀	-144.10	-126.52
MeP5…C₆H₁₄	-112.97	-100.29	MeP5…C₁₆H₃₄	-144.64	-126.98
MeP5…C₇H₁₆	-121.63	-106.82

Table 2 Binding energies of MeP5…CnH2n+2(n=1―10, 12, 14, 16)

Complex	$? E B 3 P W 91 - D 3 B J C P$ / (kJ·mol^-1)	$? E C A M - B 3 L Y P - D 3 B J C P$ / (kJ·mol^-1)	Complex	$? E B 3 P W 91 - D 3 B J C P$ / (kJ·mol^-1)	$? E C A M - B 3 L Y P - D 3 B J C P$ / (kJ·mol^-1)
MeP5…CH₄	-32.68	-30.33	MeP5…C₈H₁₈	-129.37	-113.80
MeP5…C₂H₆	-55.69	-49.62	MeP5 …C₉H₂₀	-133.43	-117.53
MeP5 …C₃H₈	-74.35	-65.73	MeP5…C₁₀H₂₂	-137.74	-121.38
MeP5…C₄H₁₀	-91.42	-81.34	MeP5…C₁₂H₂₆	-141.92	-124.77
MeP5…C₅H₁₂	-103.85	-91.17	MeP5…C₁₄H₃₀	-144.10	-126.52
MeP5…C₆H₁₄	-112.97	-100.29	MeP5…C₁₆H₃₄	-144.64	-126.98
MeP5…C₇H₁₆	-121.63	-106.82

Fig.4 Electrostatic potential of MeP5(A), C6H14(B) and MeP5…C6H14(C)

Fig.5 Geometries of MeP5…C12H26(A), models A(B) and B(C)

Table 3 Binding energies and energy components of MeP5…C12H26 in models A and B*

Complex	E_ALMO-EDA/(kJ·mol^-1)	E_Elec/(kJ·mol^-1)	E_Pauli/(kJ·mol^-1)	E_Disp/(kJ·mol^-1)	E_Pol/(kJ·mol^-1)	E_CT/(kJ·mol^-1)
MeP5…C₁₂H₂₆	-124.75	-210.48(46.06%)	332.23	-219.45(48.02%)	-15.28(3.34%)	-11.76(2.57%)
Model A	-21.18	-72.98(47.92%)	131.10	-66.15(43.44%)	-5.13(3.37%)	-8.03(5.27%)
Model B	-72.25	-136.60(47.98%)	212.49	-131.44(46.16%)	-8.26(2.90%)	-8.43(2.96%)

Fig.6 Binding energy of MeP5…C4H10 complexes at different distances

Fig.7 Gibbs free energy change(ΔG)(A) and enthalpy change(ΔH)(B) of MeP5…CnH2n+2(n=3―10, 12, 14, 16)

Table 4 ALMO-EDA energy components calculated with CAM-B3LYP-D3BJ/def2-SVPD*

Complex	E_ALMO-EDA/ (kJ·mol^-1)	E_Elec/(kJ·mol^-1)	E_Pauli/ (kJ·mol^-1)	E_Disp/(kJ·mol^-1)	E_Pol/(kJ·mol^-1)	E_CT/(kJ·mol^-1)
MeP5…CH₄	-30.34	-41.40(43.88%)	64.01	-47.75(50.61%)	-2.85(3.02%)	-2.35(2.49%)
MeP5…C₂H₆	-49.62	-80.48(46.13%)	124.83	-83.77(48.02%)	-5.79(3.32%)	-4.41(2.53%)
MeP5…C₃H₈	-65.72	-84.80(43.68%)	128.43	-99.12(51.06%)	-6.19(3.19%)	-4.04(2.08%)
MeP5…C₄H₁₀	-81.34	-107.92(43.70%)	165.62	-124.55(50.43%)	-8.51(3.44%)	-5.99(2.42%)
MeP5…C₅H₁₂	-91.17	-140.68(45.25%)	219.71	-150.93(48.55%)	-10.99(3.53%)	-8.28(2.66%)
MeP5 …C₆H₁₄	-100.28	-159.50(45.52%)	250.15	-168.81(48.17%)	-12.33(3.52%)	-9.79(2.79%)
MeP5…C₇H₁₆	-106.80	-181.70(46.40%)	284.80	-185.67(47.41%)	-13.49(3.45%)	-10.74(2.74%)
MeP5…C₈H₁₈	-113.79	-191.62(46.22%)	300.76	-197.79(47.71%)	-14.19(3.42%)	-10.95(2.64%)
MeP5…C₉H₂₀	-117.48	-199.39(46.23%)	313.78	-206.06(47.78%)	-14.59(3.38%)	-11.22(2.60%)
MeP5…C₁₀H₂₂	-121.39	-204.88(46.09%)	323.10	-213.30(47.99%)	-14.85(3.34%)	-11.46(2.58%)
MeP5…C₁₂H₂₆	-124.75	-210.48(46.06%)	332.23	-219.45(48.02%)	-15.28(3.34%)	-11.76(2.57%)
MeP5…C₁₄H₃₀	-126.53	-212.03(45.92%)	335.19	-222.26(48.14%)	-15.45(3.35%)	-11.98(2.60%)
MeP5…C₁₆H₃₄	-126.96	-212.72(45.92%)	336.25	-223.09(48.16%)	-15.50(3.35%)	-11.89(2.57%)

Fig.8 Subtracted value between the binding energy, electrostatics, dispersion, polarization and charge transfer of MeP5…CnH2n+2 and MeP5…Cn-1H2n(n=2―10, 12, 14, 16)

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