Probing the Competition among Different Coordination Motifs in Metal–Ciprofloxacin Complexes through IRMPD Spectroscopy and DFT Calculations

The vibrational spectra of ciprofloxacin complexes with monovalent (Li⁺, Na⁺, K⁺, Ag⁺) and polyvalent (Mg²⁺, Al³⁺) metal ions are recorded in the range 1000–1900 cm^–1 by means of infrared multiple-photon dissociation (IRMPD) spectroscopy. The IRMPD spectra are analyzed and interpreted in the light of density functional theory (DFT)-based quantum chemical calculations in order to identify the possible structures present under our experimental conditions. For each metal–ciprofloxacin complex, four isomers are predicted, considering different chelation patterns. A good agreement is found between the measured IRMPD spectrum and the calculated absorption spectrum of the most stable isomer for each complex. Metal ion size and charge are found to drive the competition among the different coordination motifs: small size and high charge density metal ions prefer to coordinate the quinolone between the two carbonyl oxygen atoms, whereas large-size metal ions prefer the carboxylate group as a coordination site. In the latter case, an intramolecular hydrogen bond compensates the weaker interaction established by these cations. The role of the metal cation on the stabilization of ionic and nonionic structures of ciprofloxacin is also investigated. It is found that large-size metal ions preferentially stabilize charge separated motifs and that the increase of metal ion charge has a stabilizing effect on the zwitterionic form of ciprofloxacin

Chlorine Para-Substitution of 1‑Phenylethanol: Resonant Photoionization Spectroscopy and Quantum Chemical Calculations of Hydrated and Diastereomeric Complexes

The conformational landscape of (<i>S</i>)-1-(4-chlorophenyl)­ethanol, its monohydrated complex, and its diastereomeric adducts with <i>R</i>- and <i>S</i>-butan-2-ol, have been investigated by resonant two-photon ionization (R2PI) spectroscopy coupled with time-of-flight mass spectrometry. Theoretical calculations at the D-B3LYP/6-31++G** level of theory have been performed to assist in the interpretation of the spectra and in the assignment of the structures. The R2PI spectra and the predicted structures have been compared with those obtained on the analogous non-halogenated and fluorinated systems, i.e., (<i>R</i>)-1-phenylethanol and (<i>S</i>)-1-(4-fluorophenyl)­ethanol, respectively. It appears that the presence of chlorine atom in the para position of the aromatic ring does not influence the overall geometry of bare molecule and its complexes with respect to the non-halogenated analogous systems. Anyway, it affects the electron density in the π system, and in turn the strength of OH···π and CH···π interactions. A spectral chiral discrimination is evident from the R2PI spectra of the diastereomeric adducts of (<i>S</i>)-1-(4-chlorophenyl)­ethanol with the two enantiomers of butan-2-ol