title: Conformation and molecular dynamics of single polystyrene chain confined in coordination nanospace.
abstract: Molecules confined in nanospaces will have distinctly different properties to those in the bulk state because of the formation of specific molecular assemblies and conformations. We studied the chain conformation and dynamics of single polystyrene (PSt) chains confined in highly regular one-dimensional nanochannels of a porous coordination polymer [Zn 2(bdc) 2ted] n ( 1; bdc = 1,4-benzenedicarboxylate, ted = triethylenediamine). Characterization by two-dimensional (2D) heteronuclear (1)H- (13)C NMR gave a direct demonstration of the nanocomposite formation and the intimacy between the PSt and the pore surfaces of 1. Calorimetric analysis of the composite did not reveal any glass transition of PSt, which illustrates the different nature of the PSt encapsulated in the nanochannels compared with that of bulk PSt. From N 2 adsorption measurements, the apparent density of PSt in the nanochannel was estimated to be 0.55 g cm (-3), which is much lower than that of bulk PSt. Results of a solid-state (2)H NMR study of the composite showed the homogeneous mobility of phenyl flipping with significantly low activation energy, as a result of the encapsulation of single PSt chains in one-dimensional regular crystalline nanochannels. This is also supported by molecular dynamics (MD) simulations.
authors.affiliation: Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan. kitagawa@sbchem.kyoto-u.ac.jp
authors.forename: Takashi
authors.initials: T
authors.lastname: Uemura
authors.forename: Satoshi
authors.initials: S
authors.lastname: Horike
authors.forename: Kana
authors.initials: K
authors.lastname: Kitagawa
authors.forename: Motohiro
authors.initials: M
authors.lastname: Mizuno
authors.forename: Kazunaka
authors.initials: K
authors.lastname: Endo
authors.forename: Silvia
authors.initials: S
authors.lastname: Bracco
authors.forename: Angiolina
authors.initials: A
authors.lastname: Comotti
authors.forename: Piero
authors.initials: P
authors.lastname: Sozzani
authors.forename: Masataka
authors.initials: M
authors.lastname: Nagaoka
authors.forename: Susumu
authors.initials: S
authors.lastname: Kitagawa