Covalent nanosynthesis of fluorene-based macrocycles and organic nanogrids

Gridization is an alternative way to create macromolecules of various sizes in addition to linear and dendritic polymerization as well as cyclization. Organic nanogrids are an expanding family of macrocycle-like closed structures at the nanoscale, but with a series of well-defined extension edges and vertices. Cyclic nanogrids can be used as nanoscale building blocks for the fabrication of not only rotaxanes, catenanes, knots, 3D cages, but also nanopolymers, covalent organic frameworks (COFs), metal-organic frameworks (MOFs), and complex molecular cross-scale architectures. In this review, the history of fluorene-based macrocycles has first been explored, followed by the development of the synthetic methodologies; in particular, fluorene-based nanogrids are highlighted owing to their features and applications. Typically, fluorenes are fused arenes with a hybrid entity between tetrahedral Csp³ and Csp². Four ingenious connection modes of fluorene-based macrocycles, including 2,7-, 3,6-, 9,9-, and 2,9-linkages, fully demonstrate the geometric possibilities of the macrocycles and nanogrids. Such fluorene-based nanogrids will give birth to organic intelligence.