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We performed cryogenic ion mobility-mass spectrometry (IM-MS) to study conformations of dibenzo-crown-ether complexes with Na + and K + ions at 86 K in the gas phase. Four dibenzo-crown-ethers (dibenzo-18-crown-6, dibenzo-21-crown-7, dibenzo-24-crown-8, and dibenzo-30-crown-10) with different cavity ring sizes were investigated. For dibenzo-18-crown-6 complexes with Na + and K + , only one type of conformer was assigned by comparing the experimental collision cross sections with those predicted theoretically for candidate structures. In this conformer, the distance between two benzene rings in the complexes was long due to the open form of the dibenzo-18crown-6. This open conformer was consistent with the previous laser spectroscopic studies of the cold complex ions in the gas phase. For dibenzo-21-crown-7 and dibenzo-24-crown-8 complexes with Na + and K + , two types of conformers were clearly separated by IM-MS. These two conformer types were assigned to "open" and "closed" forms in which benzene−benzene distances were long and short, respectively. Observed relative abundances of the open and closed conformers qualitatively agreed with the Boltzmann distribution using Gibbs energies of the conformers calculated by quantum chemical calculations. For the Na + (dibenzo-30-crown-10) complex, open and closed conformers were also observed in IM-MS. On the other hand, only the closed conformer was observed for the K + (dibenzo-30-crown-10) complex. This closed conformer was similar to the "wraparound" structure, which was proposed in the previous studies in the solution. In conclusion, the closed conformers were formed by the deformation of flexible crown ethers with large cavity ring sizes. In addition, the diameter of the K + ion was suitable to form the closed conformer by deformation of the molecular structure of dibenzo-30-crown-10.

Variable-temperature cryogenic ion mobility-mass spectrometry (VT-Cryo-IM-MS) was developed to examine the conformations of host-guest complexes. The VT-Cryo-IM-MS consists of an electrospray ionization source, a quadrupole ion trap, a cryogenic ion drift tube, and a time-of-flight mass spectrometer. The ion drift tube was cooled to 83 K with liquid nitrogen. Two sets of ion funnels are installed at the source and the drift tube to focus the ion beam. We used Li+-encapsulated fullerene (Li+@C60) as a reference ion to examine the ion-mobility resolution of the VT-Cryo-IM-MS apparatus because this ion has a rigid structure with a single conformer. The temperature dependence of collision cross section (CCS) of Li+@C60 and the resolution of the apparatus were determined at each temperature. We examined the conformations of host-guest complexes of a series of metal ions (M = Ca2+, Na+, Ag+, K+, Rb+, and Cs+) with dibenzo-24-crown-8 (DB24C8) by Cryo-IM-MS. All CCS distributions were fitted with two Gaussian functions which are assigned to closed and open conformers. These closed and open conformers have different distances between the two benzene rings of DB24C8. The abundance ratio of closed conformers for these M(DB24C8) complex ions depends on the guest M ion with an order, Ca2+ < Na+ < Ag+ < Cs+ < Rb+ < K+. The stability of the closed conformer of K+(DB24C8) originates from the benzene ring positional relationship which is quite close to that of the free benzene dimer. This special benzene dimer-like conformation produces the strong π-π interaction between the benzene rings of K+(DB24C8).

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