Theoretical study on the interactions between dibenzothiophene/dibenzothiophene sulfone and ionic liquids
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摘要: 采用密度泛函理论方法比较了DBT/DBTO2和[BMIM]+[PF6]-/[BMIM]+[BF4]-的相互作用。对最稳定的[BMIM]+[PF6]-、[BMIM]+[PF6]--DBT、[BMIM]+[PF6]--DBTO2、[BMIM]+[BF4]-、[BMIM]+[BF4]--DBT、[BMIM]+[BF4]--DBTO2进行了NBO和AIM分析。结果表明,DBT和[BMIM]+[PF6]-/[BMIM]+[BF4]-中的咪唑环彼此相互平行,NBO和AIM分析表明它们之间发生了π-π相互作用。H1'和H9'形成的F…H氢键有利于π-π堆积作用的形成。DBTO2倾向于趋近C2-H2和甲基基团形成O…H相互作用;DBTO2优先吸附在[BMIM]+[PF6]-/[BMIM]+[BF4]-。在模拟油中,[BMIM]+[PF6]-和[BMIM]+[BF4]-离子液体对DBTO2的萃取能力大于DBT,其原因是可能是DBTO2具有较大的极性和O…H与F…H的氢键作用。Abstract: The interactions between sulfur-containing compounds of dibenzothiophene (DBT) and dibenzothiophene sulfone (DBTO2) and ionic liquids of 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]+[PF6]-) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]+[BF4]-) were comparatively studied by using density functional theory. The most stable structures of [BMIM]+[PF6]-, [BMIM]+[PF6]--DBT, [BMIM]+[PF6]--DBTO2, [BMIM]+[BF4]-, [BMIM]+[BF4]--DBT, and [BMIM]+[BF4]--DBTO2 systems were obtained by natural bond orbitals (NBO) and atoms in molecules (AIM) analyses. The results indicated that DBT and [BMIM] rings of [BMIM]+[PF6]-/[BMIM]+[BF4]- are parallel to each other. There is a strong π-π interaction between them in terms of NBO and AIM analyses. The H1' and H9' involved F…H hydrogen bonding interactions may favor the formation of π-π stacking interactions. The DBTO2 preferentially locates near the C2-H2 and methyl group of [BMIM]+ to form O…H interactions. The predicted geometries and interaction energies imply the preferential adsorption of DBTO2 on [BMIM]+[PF6]-/[BMIM]+[BF4]-. The [BMIM]+[PF6]-/[BF4]- have better extracting ability to remove DBTO2 than DBT, possibly due to the larger polarity of DBTO2 and stronger interactions between [BMIM]+[PF6]-/[BF4]- and DBTO2.
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Key words:
- density functional theory /
- dibenzothiophene /
- dibenzothiophene sulfone /
- ionic liquid
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