Infrared spectrum of the cold ortho-fluorinated protonated neurotransmitter 2-phenylethylamine: competition between NH+center dot center dot center dot pi and NH+center dot center dot center dot F interactions

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dc.contributor.authorSchütz, Markus
dc.contributor.authorBouchet, Aude
dc.contributor.authorDopfer, Otto
dc.date.accessioned2017-10-24T06:16:59Z
dc.date.available2017-10-24T06:16:59Z
dc.date.issued2016
dc.descriptionDieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.de
dc.descriptionThis publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.en
dc.description.abstractHalogenation of pharmaceutical molecules is a common tool to modify their physiological properties. The geometric, vibrational, and electronic properties of the ortho-fluorinated protonated neurotransmitter 2-phenylethylamine (oF-H(+)PEA) are characterized by infrared photodissociation (IRPD) spectroscopy in the NH stretch range using the messenger technique and dispersion-corrected density functional theory calculations at the B3LYP-D3/aug-cc-pVTZ level to elucidate the drastic effect of site-specific ortho-fluorination. The IRPD spectra of cold oF-H(+)PEA-Rg dimers (Rg = Ne, Ar) are assigned to the most stable gauche conformer (Gf1) of oF-H(+)PEA, which benefits from both NH+center dot center dot center dot pi and NH+center dot center dot center dot F interactions. A minor contribution (similar to 5%) of the slightly less stable Gf2 gauche conformer (E-0 = +1.1 kJ mol(-1)) is also identified. Comparison of oF-H(+)PEA with unsubstituted H(+)PEA reveals a much stronger NH+center dot center dot center dot pi interaction in H(+)PEA resulting in a large red shift of the bonded NH stretch frequency. This behavior is confirmed by natural bond orbital (NBO) analysis and noncovalent interaction (NCI) calculations. The Rg ligand prefers a binding site at which it can maximize the interaction with the aromatic pi electron system and the ammonium group. Although the intermolecular interactions with the Rg atoms can compete with the noncovalent intramolecular bonds, they induce only minor spectral shifts in the NH stretch range.en
dc.description.sponsorshipEC/FP7/600209/EU/International Post-Doc Initiative of the Technische Universität Berlin/IPODIen
dc.identifier.eissn1463-9084
dc.identifier.issn1463-9076
dc.identifier.pmid27722329
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/6873
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-6212
dc.language.isoen
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titleInfrared spectrum of the cold ortho-fluorinated protonated neurotransmitter 2-phenylethylamine: competition between NH+center dot center dot center dot pi and NH+center dot center dot center dot F interactionsen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c6cp05915e
dcterms.bibliographicCitation.issue38
dcterms.bibliographicCitation.journaltitlePhysical chemistry, chemical physicsen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend26989
dcterms.bibliographicCitation.pagestart26980
dcterms.bibliographicCitation.volume18
tub.accessrights.dnbdomain
tub.affiliationFak. 2 Mathematik und Naturwissenschaften::Inst. Optik und Atomare Physik::FG Lasermolekülspektroskopie und Umweltphysikde
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Lasermolekülspektroskopie und Umweltphysikde
tub.affiliation.instituteInst. Optik und Atomare Physikde
tub.publisher.universityorinstitutionTechnische Universität Berlin

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