Reticular synthesis of porous molecular 1D nanotubes and 3D networks

Abstract

Synthetic control over pore size and pore connectivity is the crowning achievement for porous metal-organic frameworks. The same level of control has not been achieved for molecular crystals, which are not defined by strong, directional intermolecular coordination bonds. Hence, molecular crystallization is inherently less predictable than framework crystallization, and there are fewer examples of ‘reticular synthesis’, where multiple building blocks can be assembled according to a common assembly motif. Here, we apply a chiral recognition strategy to a new family of tubular covalent cages, TCC1–TCC3, to create both 1-D porous nanotubes and 3-D, diamondoid pillared porous networks in a targeted way. The diamondoid networks are analogous to metal-organic frameworks prepared from tetrahedral metal nodes and linear, difunctional organic linkers. The crystal structures can be rationalized by computational lattice energy searches, which provide an in silico screening method to evaluate candidate molecular building blocks. These results are a blueprint for applying the ‘node and strut’ principles of reticular synthesis to molecular crystals.

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Identifiers

ORCID for A. Pulido: orcid.org/0000-0002-7596-7262

ORCID for G.M. Day: orcid.org/0000-0001-8396-2771

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