Hydrogen-Bonded Fibrous Nanotubes Assembled from Trigonal Prismatic Building Blocks

In reticular chemistry, molecular building blocks are designed to create crystalline open frameworks. A key principle of reticular chemistry is that the most symmetrical networks are the likely outcomes of reactions, particularly when highly symmetrical building blocks are involved. The strategy of synthesizing low-dimensional networks aims to reduce explicitly the symmetry of the molecular building blocks. Here we report the spontaneous formation of hydrogen-bonded fibrous structures from trigonal prismatic building blocks, which were designed to form three-dimensional crystalline networks on account of their highly symmetrical structures. Utilizing different microscopic and spectroscopic techniques, we identify the structures at the early stages of the assembly process in order to and understand the growth mechanism. The symmetrical molecular building blocks are incorporated preferentially in the longitudinal direction, giving rise to anisotropic hydrogen-bonded porous organic nanotubes. Entropy-driven anisotropic growth provides micrometer-scale unidirectional nanotubes with high porosity. By combining experimental evidence and theoretical modeling, we have obtained a deep understanding of the nucleation and growth processes. Our findings offer fundamental insight into the molecular design of tubular structures. The nanotubes evolve further in the transverse directions to provide extended higher-order fibrous structures [nano- and microfibers], ultimately leading to large-scale interconnected hydrogen-bonded fiber-like structures with twists and turns. Our work provides fundamental understanding and paves the way for innovative molecular designs in low-dimensional networks.