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

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• 作者：Susanna Piccirillo ; Alessandra Ciavardini ; Enrico Bodo ; Flaminia Rondino ; Debora Scuderi ; Vincent Steinmetz ; Alessandra Paladini
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：January 7, 2013
• 年：2013
• 卷：52
• 期：1
• 页码：103-112
• 全文大小：430K
• 年卷期：v.52,no.1(January 7, 2013)
• ISSN：1520-510X

文摘

The vibrational spectra of ciprofloxacin complexes with monovalent (Li⁺, Na⁺, K⁺, Ag⁺) and polyvalent (Mg²⁺, Al³⁺) metal ions are recorded in the range 1000鈥?900 cm^鈥? 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鈥揷iprofloxacin 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.