title: Guest rotations within a capsuleplex probed by NMR and EPR techniques.
abstract: With the help of (1)H NMR and EPR techniques, we have probed the dynamics of guest molecules included within a water-soluble deep cavity cavitand known by the trivial name octa acid. All guest molecules investigated here form 2:1 (host/guest) complexes in water, and two host molecules encapsulate the guest molecule by forming a closed capsule. We have probed the dynamics of the guest molecule within this closed container through (1)H NMR and EPR techniques. The timescales offered by these two techniques are quite different, millisecond and nanosecond, respectively. For EPR studies, paramagnetic nitroxide guest molecules and for (1)H NMR studies, a wide variety of structurally diverse neutral organic guest molecules were employed. The guest molecules freely rotate along their x axis (long molecular axis and magnetic axis) on the NMR timescale; however, their rotation is slowed with respect to that in water on the EPR timescale. Rotation along the x axis is dependent on the length of the alkyl chain attached to the nitroxide probe. Overall rotation along the y or z axis was very much dependent on the structure of the guest molecule. The guests investigated could be classified into three groups: (a) those that do not rotate along the y or z axis both at room and elevated (55 degrees C) temperatures, (b) those that rotate freely at room temperature, and (c) those that do not rotate at room temperature but do so at higher temperatures. One should note that rotation here refers to the NMR timescale and it is quite possible that all molecules may rotate at much longer timescales than the one probed here. A slight variation in structure alters the rotational mobility of the guest molecules.
authors.affiliation: Department of Chemistry, University of Miami, Coral Gables, Florida 33124, USA.
authors.forename: Revathy
authors.initials: R
authors.lastname: Kulasekharan
authors.forename: Nithyanandhan
authors.initials: N
authors.lastname: Jayaraj
authors.forename: Mintu
authors.initials: M
authors.lastname: Porel
authors.forename: Rajib
authors.initials: R
authors.lastname: Choudhury
authors.forename: Arun Kumar
authors.initials: AK
authors.lastname: Sundaresan
authors.forename: Anand
authors.initials: A
authors.lastname: Parthasarathy
authors.forename: M Francesca
authors.initials: MF
authors.lastname: Ottaviani
authors.forename: Steffen
authors.initials: S
authors.lastname: Jockusch
authors.forename: N J
authors.initials: NJ
authors.lastname: Turro
authors.forename: V
authors.initials: V
authors.lastname: Ramamurthy
mesh_terms: D004578:Electron Spin Resonance Spectroscopy; D005231:Fatty Acids, Unsaturated / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D012399:Rotation; D012995:Solubility; D013499:Surface Properties; D014867:Water / Q000737:chemistry
chemical_list: D005231:Fatty Acids, Unsaturated; D014867:Water; C062198:octa-2,4,6-trienoic acid