Self-assembly of lattices with high structural complexity from a geometrically simple molecule

Abstract

Here we report an anomalous porous molecular crystal built of C–H···N-bonded double-layered roof-floor components and wall components of a segregatively interdigitated architecture. This complicated porous structure consists of only one type of fully aromatic multijoint molecule carrying three identical dipyridylphenyl wedges. Despite its high symmetry, this molecule accomplishes difficult tasks by using two of its three wedges for roof-floor formation and using its other wedge for wall formation. Although a C–H···N bond is extremely labile, the porous crystal maintains its porosity until thermal breakdown of the C–H···N bonds at 202°C occurs, affording a nonporous polymorph. Though this nonporous crystal survives even at 325°C, it can retrieve the parent porosity under acetonitrile vapor. These findings show how one can translate simplicity into ultrahigh complexity.

Supramolecular Polymers – we've Come Full Circle

“…Together with their subsequent discovery of a self-healable high-temperature porous material composed of very rare CH···N bonds, the invention of selfhealable polymer glass updated the preconception that only soft rubbery materials can heal. [89] These seminal works certainly contribute to the realization of sustainable society.…”

A Three‐Dimensional Dynamic Supramolecular “Sticky Fingers” Organic Framework

“…[2] Recently, novel synthetic strategies were proposed that diverge from classical approaches.While the latter are usually based on the temperature,p ressure,a nd exact formulation control, reac-tivity control of the former explores novel environmental strategies (for example,t he successful surface chemistry approach, [3] chemical topology, [4] or chemical reactions performed in confined spaces [5] in which the reactivity differs in many aspects from those conducted in bulk solution). In that sense,p orous materials connected by intermolecular bonds (such as,m etal-organic frameworks [6] (MOFs), covalent organic frameworks [7] (COFs), or porous molecular materials [8] that are built from discrete molecules [9] such as porous organic cages) [10] have provided notable results.The discovery and development of these materials has spurred an interest in confined chemical reactions to determine how spatial confinement can influence the yields and reactivity pathways of reactions. [11] MOFs offer improved flexibility compared to rigid zeolites and less processable COFs.…”

Polymer Networks: From Plastics and Gels to Porous Frameworks

“…Substantial progress has been made recently to enhance the crystallinity of COFs,ofwhich much focus has been placed on improving the reversibility of COF forming processes.While irreversible reactions lead to amorphous networks,o ne of the weakest interactions in nature-the van der Waals interaction-can drive organic molecules into large single crystals,some of which display intrinsic porosity. [247] Indeed, in situ polymerization of single crystals of organic monomers represents af acile approach to monocrystalline COFs through single-crystalto-single-crystal transformations. [248][249][250] In 2013, Wuest and co-workers constructed am onocrystalline COF by polymerizing tetrakis(4-nitrosophenyl)methane through the formation of azodioxy dimers, [251] which have al ow activation barrier of dissociation (20-30 kcal mol À1 ).…”