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dc.contributor.CRUESPUniversidade Estadual de Campinaspt_BR
dc.typeArtigo de periódicopt_BR
dc.titleGaseous supramolecules of imidazolium ionic liquids: "Magic" numbers and intrinsic strengths of hydrogen bondspt_BR
dc.contributor.authorGozzo, FCpt_BR
dc.contributor.authorSantos, LSpt_BR
dc.contributor.authorAugusti, Rpt_BR
dc.contributor.authorConsorti, CSpt_BR
dc.contributor.authorDupont, Jpt_BR
dc.contributor.authorEberlin, MNpt_BR
unicamp.authorUniv Fed Rio Grande Sul, Inst Chem, BR-91501970 Porto Alegre, RS, Brazil Univ Fed Minas Gerais, Inst Chem, BR-31283970 Belo Horizonte, MG, Brazil Univ Estadual Campinas, Thomson Mass Spectrometry Lab, Inst Chem, BR-13083970 Campinas, SP, Brazilpt_BR
dc.subjecthydrogen bondspt_BR
dc.subjectionic liquidspt_BR
dc.subjectkinetic methodpt_BR
dc.subjectmass spectrometrypt_BR
dc.subjectsupramolecular chemistrypt_BR
dc.subject.wosElectrospray-ionization Masspt_BR
dc.subject.wosTemperature Molten-saltspt_BR
dc.subject.wosKinetic Methodpt_BR
dc.subject.wosThermochemical Determinationspt_BR
dc.subject.wosRhodium Complexespt_BR
dc.subject.wosSerine Octamerpt_BR
dc.subject.wosCluster Ionspt_BR
dc.description.abstractElectrospray 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-).pt
dc.relation.ispartofChemistry-a European Journalpt_BR
dc.relation.ispartofabbreviationChem.-Eur. J.pt_BR
dc.publisherWiley-v C H Verlag Gmbhpt_BR 3pt_BR
dc.identifier.citationChemistry-a European Journal. Wiley-v C H Verlag Gmbh, v. 10, n. 23, n. 6187, n. 6193, 2004.pt_BR
dc.sourceWeb of Sciencept_BR
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