季铵盐对碘代全氟烷烃的卤键吸附作用

doi:10.7503/cjcu20170495

摘要/Abstract

摘要：

通过红外光谱、紫外光谱及核磁共振波谱表征了四丁基碘化铵盐对正己烷溶液中二碘四氟乙烷(C₂F₄I₂)的卤键吸附作用. 结果表明, 固液两相间卤键作用引起的光谱变化同溶液中形成卤键复合物的光谱变化一致; 四丁基氯化铵的吸附作用强于四丁基溴化铵和四丁基碘化铵, 而具有较长烷烃链的季铵盐--十六烷基三甲基氯/溴化铵对C₂F₄I₂则完全没有吸附作用. 对四丁基氯化铵与4种碘代全氟烷烃间卤键作用强度的测定结果显示, 尽管溶液中一碘代全氟烷烃与氯阴离子间的卤键作用强于二碘代全氟烷烃, 但在固液两相间四丁基氯化铵对二碘代全氟烷烃的吸附强于一碘代全氟烷烃. 利用拉曼光谱研究该体系时, 发现卤键的形成可增强碘代全氟烷烃的拉曼光谱.

关键词: 卤键, 碘代全氟烷烃, 季铵盐, 卤阴离子, 吸附

Abstract:

The adsorption of 1,2-diiodotetrafluoroethane(C₂F₄I₂) on tetrabutyl ammonium iodide(Bu₄N⁺I^-) was analyzed by IR, UV and ¹⁹F NMR spectroscopies. The according spectrum changes of IR, UV and ¹⁹F NMR indicated that halogen bond complexes were formed in solution, which demonstrated that the adsorption was due to the C-I…I^- halogen bonding interactions. The adsorptivities of five quaternary ammonium salts were compared and the experiment results showed that adsorptivity was Bu₄N⁺Cl^->Bu₄N⁺Br^->Bu₄N⁺I^-. Hexadecyl trimethyl ammonium chloride and hexadecyl trimethyl ammonium bromide, which have long alkyl chain, had absolutely no adsorption to C₂F₄I₂. It is probably because that the long alkyl chains prevented halide anion from closing to C₂F₄I₂. The adsorption of four iodoperfluoroalkanes(C₄F₈I₂, C₄F₉I, C₆F₁₂I₂, C₆F₁₃I) by Bu₄N⁺Cl^- salt were investigated. The results showed that although halogen bonds in the monoiodoperfluoroalkanes(monoiodo-PFAs) complexes were stronger than those in the diiodoperfluoroalkanes(diiodo-PFAs) complexes as estimated by Raman spectra in solution, the adsorptivities of Bu₄N⁺Cl^- for the diiodo-PFAs were stronger than those for the monoiodo-PFAs at the solid/liquid interface because the odds of forming halogen bond of diiodo-PFAs is double that of monoiodo-PFAs. Besides, it was found that the formation of halogen bonds could enhance the Raman signals of iodoperfluoroalkanes.

Key words: Halogen bond, Iodoperfluoroalkane, Tetrabutyl ammonium halide, Halide anion, Adsorption

中图分类号:

O647

TrendMD:

阎小青, 刘秋双, 刘云凤, 牛侨. 季铵盐对碘代全氟烷烃的卤键吸附作用. 高等学校化学学报, 2018, 39(4): 743.

YAN Xiaoqing, LIU Qiushuang, LIU Yunfeng, NIU Qiao. Adsorption of Iodoperfluoroalkanes on Tetrabutyl Ammonium Halide by Halogen Bond^†. Chem. J. Chinese Universities, 2018, 39(4): 743.

图/表 8

Fig.1 FTIR spectra of C2F4I2(a), Bu4N+I-(b) and the Bu4N+I- with absorption of C2F4I2(c)

Fig.2 UV spectra of C2F4I2(a), Bu4N+I-(b) and Bu4NI + C2F4I2 in CHCl3(c)

Table 1 IR frequencies of C2F4I2 before and after being adsorbed by Bu4N+I-

Compound	ν_C-F /cm^-1			ν_C-C /cm^-1
C₂F₄I₂	1206.7	1159.9	1109.4	976.3
Adsorbed C₂F₄I₂	1168.7	1123.2	1089.3	None

Fig.3 UV spectra of C2F4I2(2 mmol/L)(a), Bu4N+I-(0.02 mmol/L)(b) and the mix solution of Bu4N+I-(0.02 mmol/L) and C2F4I2(c-g) in CHCl3c(C2F4I2)/(mmol·L-1): c. 2; d. 4; e. 6; f. 8; g. 10.

Fig.4 UV spectra of C2F4I2 in hexane solution before and after addition of different quaternary ammonium salts

Fig.5 UV spectra of the CnF2nIn in hexane before(a) and after(b) the addition of Bu4N+Cl- salt(A) C4F8I2; (B) C6F12I2; (C) C4F9I; (D) C6F13I.

Fig.6 Raman spectra of CnF2nIn(0.1 mol/L) and CnF2nIn∙Cl-(0.1 mol/L) complexes in CH3CN(A) C4F8I2; (B) C6F12I2; (C) C4F9I; (D) C6F13I. a. CnF2nIn; b. CnF2nIn ∙Cl- complexes.

Table 2 Raman frequency shifts for the C-I stretching modes of the CnF2nIn before and after adding Bu4N+Cl- in CH3CN*

Compound	$ν C — I (C n F 2 n I n)$	$ν C — I (C n F 2 n I n · C l -)$	Δ $ν C — I *$ /cm^-1
C₄F₈I₂	271.8	261.2	10.6
C₄F₉I	281.3	266.0	15.3
C₆F₁₂I₂	276.6	263.2	13.4
C₆F₁₃I	280.4	265.1	15.3

Table 2 Raman frequency shifts for the C-I stretching modes of the CnF2nIn before and after adding Bu4N+Cl- in CH3CN*

Compound	$ν C — I (C n F 2 n I n)$	$ν C — I (C n F 2 n I n · C l -)$	Δ $ν C — I *$ /cm^-1
C₄F₈I₂	271.8	261.2	10.6
C₄F₉I	281.3	266.0	15.3
C₆F₁₂I₂	276.6	263.2	13.4
C₆F₁₃I	280.4	265.1	15.3

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