title: Alkali Cation Chelation in Cold β-O-4 Tetralignol Complexes.
abstract: We employ cold ion spectroscopy (UV action and IR-UV double resonance) in the gas phase to unravel the qualitative structural elements of G-type alkali metal cationized (X = Li(+), Na(+), K(+)) tetralignol complexes connected by β-O-4 linkages. The conformation-specific spectroscopy reveals a variety of conformers, each containing distinct infrared spectra in the OH stretching region, building on recent studies of the neutral and alkali metal cationized β-O-4 dimers. The alkali metal ion is discovered to bind in penta-coordinate pockets to ether and OH groups involving at least two of the three β-O-4 linkages. Different binding sites are distinguished from one another by the number of M(+)···OH···O interactions present in the binding pocket, leading to characteristic IR transitions appearing below 3550 cm(-1). This interaction is mitigated in the major conformer of the K(+) adduct, demonstrating a clear impact of the size of the charge center on the three-dimensional structure of the tetramer.
authors.affiliation: Department of Chemistry, Purdue University , West Lafayette, Indiana 47907-2084, United States.
authors.forename: Andrew F
authors.initials: AF
authors.lastname: DeBlase
authors.affiliation: Department of Chemistry, Purdue University , West Lafayette, Indiana 47907-2084, United States.
authors.forename: Eric T
authors.initials: ET
authors.lastname: Dziekonski
authors.affiliation: Department of Chemistry, Purdue University , West Lafayette, Indiana 47907-2084, United States.
authors.forename: John R
authors.initials: JR
authors.lastname: Hopkins
authors.affiliation: Department of Chemistry, Purdue University , West Lafayette, Indiana 47907-2084, United States.
authors.forename: Nicole L
authors.initials: NL
authors.lastname: Burke
authors.affiliation: Department of Chemistry, Purdue University , West Lafayette, Indiana 47907-2084, United States.
authors.forename: Huaming
authors.initials: H
authors.lastname: Sheng
authors.affiliation: Department of Chemistry, Purdue University , West Lafayette, Indiana 47907-2084, United States.
authors.forename: Hilkka I
authors.initials: HI
authors.lastname: Kenttämaa
authors.affiliation: Department of Chemistry, Purdue University , West Lafayette, Indiana 47907-2084, United States.
authors.forename: Scott A
authors.initials: SA
authors.lastname: McLuckey
authors.affiliation: Department of Chemistry, Purdue University , West Lafayette, Indiana 47907-2084, United States.
authors.forename: Timothy S
authors.initials: TS
authors.lastname: Zwier