Kinetics of molecular transport in a nanoporous crystal studied by confocal Raman microspectrometry: single-file diffusion in a densely filled tunnel.

Confocal Raman microspectrometry has been used as an in situ probe of the transport of guest molecules along the one-dimensional tunnels in a crystalline urea inclusion compound, under conditions of guest exchange in which "new" guest molecules (pentadecane) are introduced at one end of the tunnel and displace the "original" guest molecules (1,8-dibromooctane). The Raman spectra, recorded as a function of position along the tunnel direction and as a function of time, have been used to establish details of the kinetics of the guest transport process. In particular, the transport of the new pentadecane guest molecules along the tunnel is found to exhibit a linear dependence on time, with the rate of the process in the region of 70-100 nm s-1. Mechanistic aspects relating to the guest transport process are discussed.