Gaseous supramolecules of imidazolium ionic liquids: "Magic" numbers and intrinsic strengths of hydrogen bonds

被引:225
作者
Gozzo, FC
Santos, LS
Augusti, R
Consorti, CS
Dupont, J
Eberlin, MN [1 ]
机构
[1] Univ Fed Rio Grande do Sul, Inst Chem, BR-91501970 Porto Alegre, RS, Brazil
[2] Univ Fed Minas Gerais, Inst Chem, BR-31283970 Belo Horizonte, MG, Brazil
[3] Univ Estadual Campinas, Thomson Mass Spectrometry Lab, Inst Chem, BR-13083970 Campinas, SP, Brazil
关键词
hydrogen bonds; ionic liquids; kinetic method; mass spectrometry; supramolecular chemistry;
D O I
10.1002/chem.200305742
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Electrospray ionization mass spectrometry (ESI-MS) is found to gently and efficiently transfer small to large as well as singly to multiply charged [X+](n)[A(-)](m) supramolecules of imidazolium ion (XI) ionic liquids to the gas phase, and to reveal "magic numbers" for their most favored assemblies. Tandem mass spectrometric experiments (ESI-MS/MS) were then used to dissociate, via low-energy collision activation, mixed and loosely bonded [A-----X-----A'](-) and [X-----A-----X'](+) gaseous supramolecules, as well as their higher homologues, and to estimate and order via Cooks' kinetic method (CKM) and B3LYP/6-311G(d,p) calculations the intrinsic solvent-free magnitude of hydrogen bonds. For the five anions studied, the relative order of intrinsic hydrogen-bond strengths to the 1-n-butyl-3-methylimidazolium ion [X-1](+) is: CF3CO2- (zero) > BF4- (-3.1) > PF6- (-10.0) > InCl4- (-16.4) and BPh4- (-17.6 kcal mol(-1)). The relative hydrogen-bond strength for InCl4- was measured via CKM whereas those for the other anions were calculated and used as CKM references. A good correlation coefficient (R=0.998) between fragment ion ratios and calculated hydrogen-bond strengths and an effective temperature (T-eff) of 430 K demonstrate the CKM reliability for measuring hydrogen-bond strengths in gaseous ionic liquid supramolecules. Using CKM and T-eff of 430 K, the intrinsic hydrogen-bond strengths of BF4- for the three cations investigated is: 1-n-butyl-3-methyl-imidazolium ion (0) > 1,3-di-[(R)-3-methyl-2-butyl]-imidazolium ion (-2.4) > 1,3-di-[(R)-alpha-methyl-benzyl]-imidazolium ion (-3.0 kcal mol(-1)). As evidenced by "magic" numbers, greater stabilities are found for the [(X-1)(2)(BF4)(3)](-) and [(X-1)(5)A(4)](+) supramolecules (A not equal InCl4-).
引用
收藏
页码:6187 / 6193
页数:7
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