In this critical review we survey non-covalent interactions of carbon nanotubes with molecular species from a chemical perspective, particularly emphasising the relationship between the structure and dynamics of these structures and their functional properties. We demonstrate the synergistic character of the nanotube-molecule interactions, as molecules that affect nanotube properties are also altered by the presence of the nanotube. The diversity of mechanisms of molecule-nanotube interactions and the range of experimental techniques employed for their characterisation are illustrated by examples from recent reports. Some practical applications for carbon nanotubes involved in non-covalent interactions with molecules are discussed.

This Account focuses on structural and dynamic behavior of molecules encapsulated in carbon nanotubes. The impact of the confinement on the molecular packing, orientation, translation, rotation, and reactivity is demonstrated for a range of fullerene and nonfullerene molecules. These phenomena are described and analyzed using the current understanding of molecule-nanotube and intermolecular interactions.

We have assembled molecular arrays of C60 inside double-walled carbon nanotubes (DWNTs) with internal diameters of 11-26 A and directly observed the existence of different crystalline phases of C60 previously predicted theoretically. The structure of the encapsulated C60 crystal is defined by the internal diameter of the DWNT, as the molecules adjust their packing arrangement in order to maximize van der Waals interactions. We have also shown that fullerenes in C(60)@DWNT interact with the outer layer of DWNTs, as demonstrated by the efficient filling of DWNTs with internal diameters of less than 12 A.