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Chirality Effects on the IRMPD Spectra of Basket Resorcinarene/Nucleoside Complexes
Author(s) -
Filippi Antonello,
Fraschetti Caterina,
Piccirillo Susanna,
Rondino Flaminia,
Botta Bruno,
D'Acquarica Ilaria,
Calcaterra Andrea,
Speranza Maurizio
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201200614
Subject(s) - chemistry , infrared multiphoton dissociation , protonation , crystallography , stereochemistry , spectral line , infrared spectroscopy , photochemistry , molecule , physics , organic chemistry , ion , astronomy
The IRMPD spectra of the ESI‐formed proton‐bound complexes of the R,R,R,R ‐ and S,S,S,S ‐enantiomers of a bis(diamido)‐bridged basket resorcin[4]arene ( R and S ) with cytosine ( 1 ), cytidine ( 2 ), and cytarabine ( 3 ) were measured in the region 2800–3600 cm −1 . Comparison of the IRMPD spectra with the corresponding ONIOM (B3LYP/6‐31(d):UFF)‐calculated absorption frequencies allowed the assessment of the vibrational modes that are responsible for the observed spectroscopic features. All of the complexes investigated, apart from [ R⋅ H ⋅3 ] + , showed similar IRMPD spectra, which points to similar structural and conformational landscapes. Their IRMPD spectra agree with the formation of several isomeric structures in the ESI source, wherein the N(3)‐protonated guest establishes noncovalent interactions with the host amidocarbonyl groups that are either oriented inside the host cavity or outside it between one of the bridged side‐chains and the upper aromatic nucleus. The IRMPD spectrum of the [ R⋅ H ⋅3 ] + complex was clearly different from the others. This difference is attributed to the effect of intramolecular hydrogen‐bonding interactions between the C(2′)OH group and the aglycone oxygen atom of the nucleosidic guest upon repulsive interactions between the same oxygen atom and the aromatic rings of the host.