Spectroscopic Discrimination of Diastereomeric Complexes Involving an Axially Chiral Receptor

Antonello Filippi, Caterina Fraschetti, Laura Guarcini, Costantino Zazza, Tadashi Ema, Maurizio Speranza

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The infrared multiphoton dissociation (IRMPD) spectra of electrospray ionization (ESI)-formed proton-bound complexes between the axially chiral multifunctional macrocycle MaR and d- and l-phenylalanine (PD and PL) or d- and l-3,4-dihydroxyphenylalanine (DD and DL) are recorded in the (Formula presented.) =2800–3700 cm−1 region. Whereas the diastereomeric [MaR⋅H⋅PD]+ and [MaR⋅H⋅PL]+ complexes do not show any significant spectral differences, the spectrum of [MaR⋅H⋅DD]+ clearly diverges from that of its [MaR⋅H⋅DL]+ diastereomer. A comparison of the experimental spectra with the B3LYP/6-31G**-calculated harmonic vibrational frequencies of a number of stable structures indicates the formation, in the ESI source, of very similar spectroscopically active structures, with the protonated amino acid placed outside the flat cavity of the macrocycle and hydrogen-bonded at its O2 center. Different spectral signatures of the [MaR⋅H⋅DD]+ and [MaR⋅H⋅DL]+ complexes are attributed to the coexistence of several stable rotamers in the ESI source.

Original languageEnglish
Pages (from-to)2475-2481
Number of pages7
JournalChemPhysChem
Volume18
Issue number18
DOIs
Publication statusPublished - Sep 20 2017

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Keywords

  • chirality
  • IR spectroscopy
  • macrocycles
  • noncovalent interactions
  • rotamers

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

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