Direct imaging of the structure, relaxation, and sterically constrained motion of encapsulated tungsten polyoxometalate lindqvist ions within carbon nanotubes.
The imaging properties and observation of the sterically regulated translational motion of discrete tungsten polyoxometalate Linqvist ions (i.e., [W(6)O(19)](2-)) within carbon nanotubes of specific internal diameter are reported. The translational motion of the nonspheroidal anion within the nanotube capillary is found to be impeded by its near-perfect accommodation to the internal van der Waals surface of the nanotube wall. Rotational motion of the anion about one remaining degree of freedom permits translational motion of the anion along the nanotube followed by locking in at sterically favorable positions in a mechanism similar to a molecular ratchet. This steric locking permits the successful direct imaging of the constituent octahedral cation template of individual [W(6)O(19)](2-) anions by high resolution transmission electron microscopy thereby permitting meterological measurements to be performed directly on the anion. Direct imaging of pairs of equatorial W(2) atoms within the anion reveal steric relaxation of the anion contained within the nanotube capillary relative to the bulk anion structure.
Sloan
Jeremy
J
Queen Mary, University of London, Department of Engineering and Materials, Mile End Road, London, UK. j.sloan@qmul.ac.uk
Matthewman
Gemma
G
Dyer-Smith
Clare
C
Sung
A-Young
AY
Liu
Zheng
Z
Suenaga
Kazu
K
Kirkland
Angus I
AI
Flahaut
Emmanuel
E
D003460:Crystallization / Q000379:methods*; D046911:Macromolecular Substances / Q000737:chemistry; D008422:Materials Testing; D046529:Microscopy, Electron, Transmission / Q000379:methods*; D008968:Molecular Conformation; D036103:Nanotechnology / Q000379:methods*; D037742:Nanotubes, Carbon / Q000737:chemistry* / Q000648:ultrastructure*; D010316:Particle Size; D013499:Surface Properties; D014414:Tungsten / Q000737:chemistry*; D017973:Tungsten Compounds / Q000737:chemistry*; D000099294:Polyoxometalates
D046911:Macromolecular Substances; D037742:Nanotubes, Carbon; D014414:Tungsten; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates