Ultraviolet Photodissociation Spectroscopy of Cold K+•Calix[4]arene Complex in the Gas Phase

Inokuchi Yoshiya

Soga Kazuki

Hirai Kenta

Kida Motoki

Morishima Fumiya

Ebata Takayuki

Journal of Physical Chemistry A

The cooling of ionic species in the gas phase greatly simplifies the UV spectrum, which is of special importance to study the electronic and geometric structures of large systems, such as bio-related molecules and host-guest complexes. Many efforts have been devoted to achieving the ion cooling with a cold quadrupole Paul ion trap (QIT), but one problem was insufficient cooling of ions (up to ~30 K) in the QIT. In this study, we construct a mass spectrometer for ultraviolet photodissociation (UVPD) spectroscopy of gas-phase cold ions. The instrument consists of an electrospray ion source, a QIT cooled with a He cryostat, and a time-of-flight mass spectrometer. Giving a great care for the cooling condition, we can achieve ~10 K for the vibrational temperature of ions in the QIT, which is estimated from UVPD spectra of the benzo-18-crown-6 (B18C6) complex with potassium ion, K+•B18C6. Using this setup, we measure a UVPD spectrum of cold calix[4]arene (C4A) complex with potassium ion, K+•C4A. The spectrum shows a very weak band and a strong one at 36018 and 36156 cm–1, respectively, accompanied by many sharp vibronic bands in the 36000–36600 cm–1 region. In the geometry optimization of the K+•C4A complex, we obtain three stable isomers: one endo and two exo forms. On the basis of the total energy and UV spectral patterns predicted by density functional theory calculations, we attribute the structure of the K+•C4A complex to the endo isomer (C2 symmetry), in which the K+ ion is located inside the cup of C4A. The vibronic bands of K+•C4A at 36018 and 36156 cm–1 are assigned to the S1(A)–S0(A) and S2(B)–S0(A) transitions of the endo isomer, respectively.

calix[4]arene

alkali metal

ion trap

electrospray

ultraviolet

conformation

Chemistry [ 430 ]

eng

American Chemical Society

Copyright (c) 2015 American Chemical Society

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpca.5b05328.

[ISSN] 1089-5639

[ISSN] 1520-5215

[DOI] 10.1021/acs.jpca.5b05328

[DOI] https://doi.org/10.1021/acs.jpca.5b05328