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Article: Resonance Raman characterization of the different forms of ground-state 8-substituted 7-hydroxyquinoline caged acetate compounds in aqueous solutions

TitleResonance Raman characterization of the different forms of ground-state 8-substituted 7-hydroxyquinoline caged acetate compounds in aqueous solutions
Authors
Issue Date2010
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpca
Citation
Journal Of Physical Chemistry A, 2010, v. 114 n. 7, p. 2498-2505 How to Cite?
AbstractTo investigate the substituent effect on the distribution of the forms of the ground-state species of 8-substituted 7-hydroxyquinolines, ultraviolet-absorption and resonance Raman experiments were performed for 8-chloro7-hydroxyquinoline (CHQ-OAc) and 8-cyano-7-hydroxyquinoline (CyHQ-OAc) in acetonitrile (MeCN), in NaOH-H 2O/MeCN (60:40, v/v, pH 11-12), and in H 2O/MeCN (60:40, v/v, pH 6-7) solutions, and these results were compared to those previously reported for the 8-bromo-7-hydroxyquinoline (BHQ-OAc) compound. Swapping a bromine atom in BHQ-OAc for a chlorine atom in CHQ-OAc causes the amount of the tautomeric species to become larger, although the neutral species is still the predominant species for both systems in water-rich solutions. The absorption spectra and the resonance Raman spectra of CyHQ-OAc suggest that, because of the strong electron-withdrawing nature of the cyano substituent, a measurable amount of the anionic species is present and the tautomeric species cannot be easily detected in water-rich solutions. The results reported here reveal large substituent effects on the distribution of the different forms of the XHQ-OAc compounds in largely aqueous solutions. The steric effect of the 8-substituted group and competitive hydrogen bonding between the 8-substituted group and water molecules hinders the formation of a cyclic BHQ-OAc-water complex, and the electron-withdrawing property of the 8-substituted group enhances the deprotonation of the phenol group while disfavoring the formation of the positively charged quinoline nitrogen. We briefly discuss the implications of the substituent effects for using these compounds as phototriggers. © 2010 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/168437
ISSN
2015 Impact Factor: 2.883
2015 SCImago Journal Rankings: 1.231
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorAn, HYen_US
dc.contributor.authorMa, Cen_US
dc.contributor.authorLi, Wen_US
dc.contributor.authorHarris, KTen_US
dc.contributor.authorDore, TMen_US
dc.contributor.authorPhillips, DLen_US
dc.date.accessioned2012-10-08T03:18:56Z-
dc.date.available2012-10-08T03:18:56Z-
dc.date.issued2010en_US
dc.identifier.citationJournal Of Physical Chemistry A, 2010, v. 114 n. 7, p. 2498-2505en_US
dc.identifier.issn1089-5639en_US
dc.identifier.urihttp://hdl.handle.net/10722/168437-
dc.description.abstractTo investigate the substituent effect on the distribution of the forms of the ground-state species of 8-substituted 7-hydroxyquinolines, ultraviolet-absorption and resonance Raman experiments were performed for 8-chloro7-hydroxyquinoline (CHQ-OAc) and 8-cyano-7-hydroxyquinoline (CyHQ-OAc) in acetonitrile (MeCN), in NaOH-H 2O/MeCN (60:40, v/v, pH 11-12), and in H 2O/MeCN (60:40, v/v, pH 6-7) solutions, and these results were compared to those previously reported for the 8-bromo-7-hydroxyquinoline (BHQ-OAc) compound. Swapping a bromine atom in BHQ-OAc for a chlorine atom in CHQ-OAc causes the amount of the tautomeric species to become larger, although the neutral species is still the predominant species for both systems in water-rich solutions. The absorption spectra and the resonance Raman spectra of CyHQ-OAc suggest that, because of the strong electron-withdrawing nature of the cyano substituent, a measurable amount of the anionic species is present and the tautomeric species cannot be easily detected in water-rich solutions. The results reported here reveal large substituent effects on the distribution of the different forms of the XHQ-OAc compounds in largely aqueous solutions. The steric effect of the 8-substituted group and competitive hydrogen bonding between the 8-substituted group and water molecules hinders the formation of a cyclic BHQ-OAc-water complex, and the electron-withdrawing property of the 8-substituted group enhances the deprotonation of the phenol group while disfavoring the formation of the positively charged quinoline nitrogen. We briefly discuss the implications of the substituent effects for using these compounds as phototriggers. © 2010 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpcaen_US
dc.relation.ispartofJournal of Physical Chemistry Aen_US
dc.subject.meshAcetates - Chemistryen_US
dc.subject.meshComputer Simulationen_US
dc.subject.meshHydroxyquinolines - Chemistryen_US
dc.subject.meshMolecular Structureen_US
dc.subject.meshSolutionsen_US
dc.subject.meshSpectrum Analysis, Ramanen_US
dc.subject.meshWater - Chemistryen_US
dc.titleResonance Raman characterization of the different forms of ground-state 8-substituted 7-hydroxyquinoline caged acetate compounds in aqueous solutionsen_US
dc.typeArticleen_US
dc.identifier.emailMa, C:macs@hkucc.hku.hken_US
dc.identifier.emailPhillips, DL:phillips@hku.hken_US
dc.identifier.authorityMa, C=rp00758en_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/jp911143een_US
dc.identifier.pmid20113003-
dc.identifier.scopuseid_2-s2.0-77249166546en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-77249166546&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume114en_US
dc.identifier.issue7en_US
dc.identifier.spage2498en_US
dc.identifier.epage2505en_US
dc.identifier.isiWOS:000274578200011-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridAn, HY=54411879800en_US
dc.identifier.scopusauthoridMa, C=7402924979en_US
dc.identifier.scopusauthoridLi, W=36068145000en_US
dc.identifier.scopusauthoridHarris, KT=15837099400en_US
dc.identifier.scopusauthoridDore, TM=6603830858en_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US

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