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dc.contributor.author
Borba, Ana  
dc.contributor.author
Gomez Zavaglia, Andrea  
dc.contributor.author
Fausto, Rui  
dc.date.available
2016-12-29T20:12:54Z  
dc.date.issued
2013-01  
dc.identifier.citation
Borba, Ana; Gomez Zavaglia, Andrea; Fausto, Rui; Conformational Landscape, Photochemistry, and Infrared Spectra of Sulfanilamide; American Chemical Society; Journal Of Physical Chemistry A; 117; 4; 1-2013; 704-717  
dc.identifier.issn
1089-5639  
dc.identifier.uri
http://hdl.handle.net/11336/10644  
dc.description.abstract
A combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(3df,3pd) study of sulfanilamide (SA) was performed. The full conformational search on the potential energy surface of the compound allowed the identification of four different minima, all of them bearing the sulfamide nitrogen atom placed in the perpendicular orientation relatively to the aromatic ring and differing from each other in the orientation of the hydrogen atoms connected to the two nitrogen atoms of the molecule. All conformers were predicted to be significantly populated in the gas phase (at 100 °C, their relative populations were estimated as being 1:0.9:0.3:0.2). However, in agreement with the theoretically calculated low-energy barriers for conformational isomerization, in the low-temperature matrices, only the most stable conformer could be observed, with the remaining forms being converted into this form during matrix deposition (conformational cooling). The unimolecular photochemistry of matrix-isolated SA (in both argon and xenon) was also investigated. Upon broadband UV irradiation (λ > 215 nm), two photofragmentation pathways were observed: the prevalent pathway (A), leading to extrusion of sulfur dioxide and simultaneous formation of benzene-1,4-diamine, which then converts to 2,5-cyclohexadiene-1,4-diimine, and the minor pathway (B), conducting an γ-cleavage plus [1,3] H-atom migration from the sulfamide group to the aromatic ring, which leads to formation of iminosulfane dioxide and aniline, the latter undergoing subsequent phototransformation into cyclohexa-2,5-dien-1-imine. Finally, the crystalline polymorph of SA resulting from warming (265 K) the amorphous solid obtained from fast cooling of the vapor of the compound onto the cold (13 K) substrate of the cryostat was identified spectroscopically, and found to be the γ-crystalline phase, the one exhibiting in average longer H-bonds and an infrared spectrum resembling more that of the low temperature SA glass. Full assignment of the infrared spectra of this crystalline variety as well as of those of the β-polymorph room temperature crystalline sample and low temperature amorphous state was undertaken with help of theoretical results obtained for the crystallographically relevant dimer of SA.  
dc.format
application/pdf  
dc.language.iso
eng  
dc.publisher
American Chemical Society  
dc.rights
info:eu-repo/semantics/openAccess  
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/  
dc.subject
Ftir  
dc.subject
Matrix Isolation  
dc.subject
Sulfanilamide  
dc.subject.classification
Otras Ingenierías y Tecnologías  
dc.subject.classification
Otras Ingenierías y Tecnologías  
dc.subject.classification
INGENIERÍAS Y TECNOLOGÍAS  
dc.title
Conformational Landscape, Photochemistry, and Infrared Spectra of Sulfanilamide  
dc.type
info:eu-repo/semantics/article  
dc.type
info:ar-repo/semantics/artículo  
dc.type
info:eu-repo/semantics/publishedVersion  
dc.date.updated
2016-12-12T14:10:15Z  
dc.identifier.eissn
1520-5215  
dc.journal.volume
117  
dc.journal.number
4  
dc.journal.pagination
704-717  
dc.journal.pais
Estados Unidos  
dc.journal.ciudad
Washington  
dc.description.fil
Fil: Borba, Ana. Universidad de Coimbra; Portugal  
dc.description.fil
Fil: Gomez Zavaglia, Andrea. Universidad de Coimbra; Portugal. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Centro de Investigaciones en Criotecnología de Alimentos (i); Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas; Argentina  
dc.description.fil
Fil: Fausto, Rui. Universidad de Coimbra; Portugal  
dc.journal.title
Journal Of Physical Chemistry A  
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/jp311789f  
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp311789f