Insight into the behaviors of molecules in confined space is highly desired for the deep understanding of the mechanism of chemical reactions in a microenvironment. Yet the direct access of molecular evolutions at atomic resolution in nanoconfinements is still challenging. Among various guests, atomically precise clusters with well-defined structures are better suited for monitoring the chemical and physical processes in nanochannels because of their visibility under electron microscopy and identical structures that ensure homogeneous interactions. Developing an efficient method for assembling clusters into a confined space is essential for advancing mechanisms of these processes. In this Perspective, we provide an overview of the assembly of clusters into single-walled carbon nanotubes (SWCNTs) in the liquid phase. We begin with the introduction of assembling methodologies, followed by a discussion of mechanisms of confined assembly in liquids. The host-guest interactions between clusters and nanotubes and the molecular reactions in nanochannels revealed by transmission electron microscopy are unveiled, and the cluster@SWCNT heterostructure-based emerging applications are highlighted. At the end, we discuss the challenges and opportunities and expound our outlook in this field.
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