Conformation of K⁺(Crown Ether) Complexes Revealed by Ion Mobility–Mass Spectrometry and Ultraviolet Spectroscopy

Abstract

The conformation and electronic structure of dibenzo-24-crown-8 (DB24C8) complexes with K + ion were examined by ion mobility−mass spectrometry (IM−MS), ultraviolet (UV) photodissociation (UVPD) spectroscopy in the gas phase, and fluorescence spectroscopy in solution. Three structural isomers of DB24C8 (SymDB24C8, Asym1DB24C8, and Asym2DB24C8) in which the relative positions of the two benzene rings were different from each other were investigated. The IM−MS results at 86 K revealed a clear separation of two sets of conformers for the K + (SymDB24C8) and K + (Asym1DB24C8) complexes whereas the K + (Asym2DB24C8) complex revealed only one set. The two sets of conformers were attributed to the open and closed forms in which the benzene−benzene distances in the complexes were long (>6 Å) and short (<6 Å), respectively. IM−MS at 300 K could not separate the two conformer sets of the K + (SymDB24C8) complex because the interconversion between the open and closed conformations occurred at 300 K and not at 86 K. The crown cavity of DB24C8 was wrapped around the K + ion in the complex, although the IM−MS results availed direct evidence of rapid cavity deformation and the reconstruction of stable conformers at 300 K. The UVPD spectra of the K + (SymDB24C8) and K + (Asym1DB24C8) complexes at ∼10 K displayed broad features that were accompanied by a few sharp vibronic bands, which were attributable to the coexistence of multiple conformers. The fluorescence spectra obtained in a methanol solution suggested that the intramolecular excimer was formed only in K + (SymDB24C8) among the three complexes because only SymDB24C8 could possibly assume a parallel configuration between the two benzene rings upon K + encapsulation. The encapsulation methods for K + ion (the "wraparound" arrangement) are similar in the three structural isomers of DB24C8, although the difference in the relative positions of the two benzene rings affected the overall cross-section. This study demonstrated that temperature-controlled IM−MS coupled with the introduction of appropriate bulky groups, such as aromatic rings to host molecules, could reveal the dynamic aspects of encapsulation in host−guest systems.

Conformer Separation of Dibenzo-Crown-Ether Complexes with Na+ and K+ Ions Studied by Cryogenic Ion Mobility-Mass Spectrometry

“…The details of experimental apparatus of IM-MS were given elsewhere. , The M + (DB18C6), M + (DB21C7), M + (DB24C8), and M + (DB30C10) (M = Na and K) complexes were produced by electrospray ionization (ESI) of methanol solutions of 0.1 mM NaCl or KCl salt and dibenzo-crown-ethers. Ions were transferred into the first vacuum chamber through a heated metal capillary (∼330 K).…”

“…For example, isomers of cluster ions (carbon, − silicon, , water, , metal oxide , ) were separated by this method. Moreover, cryogenic IM-MS was performed by several researchers using a drift tube cooled by liquid nitrogen. − Recently, we have separated two isomers of K + (DB24C8) complexes by cryogenic IM-MS at 86 K . Two isomers were assigned to closed and open conformers in which benzene–benzene distances were short and long, respectively.…”

Conformation of Benzo-12-Crown-4 Complexes with Ammonium Ions Investigated by Cold Gas-Phase Spectroscopy

“…The conformation of the CE complexes was initially investigated using X-ray diffraction of the crystals. Recently, gas-phase IR spectroscopy was performed to reveal the conformation of the CE complexes with metal ions. − For benzo-CE complexes, UV spectroscopy under cold gas-phase conditions provided information on the conformation. − These complexes showed sharp vibronic structures in their UV spectra, allowing the application of UV–UV and IR–UV double-resonance spectroscopy to examine the number of conformers and their structures. For molecular ion guests, ammonium ions containing the NH 3 + group also form stable complexes with CEs. ,− For CE complexes with molecular ion guests, IR spectroscopy in the gas phase was performed for ammonium ions and protonated amino acids. ,, Recently, we studied dibenzo-18-crown-6 (DB18C6) complexes with primary alkylammonium ions (RNH 3 + ) by cold UV spectroscopy in the gas phase .…”

“…The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.1c09091. UVPD spectra of the EtNH 3 + (B12C4) and PrNH 3 + (B12C4) complexes observed under IR laser irradiation; stable structures of the B12C4 complexes with ammonium ions; and full list of the authors for refs , (PDF) …”

“…UVPD spectra of the EtNH 3 + (B12C4) and PrNH 3 + (B12C4) complexes observed under IR laser irradiation; stable structures of the B12C4 complexes with ammonium ions; and full list of the authors for refs , (PDF)…”