Bottom-Up Solid-State Molecular Assembly via Guest-Induced Intermolecular Interactions

Abstract

The manipulation of molecular motions to construct highly ordered supramolecular architectures from chaos in the solid state is considered to be far more complex and challenging in comparison to that in solution. In this work, a bottom-up molecular assembly approach based on a newly designed skeleton-trimmed pillar[5]­arene analogue, namely the permethylated leggero pillar[5]­arene MeP­[5]­L, is developed in the solid state. An amorphous powder of MeP­[5]­L can take up certain guest vapors to form various ordered linker-containing solid-state molecular assemblies, which can be further used to construct a thermodynamically favored linker-free superstructure upon heating. These approaches are driven by vapor-induced solid-state molecular motions followed by a thermally triggered phase-to-phase transformation. The intermolecular interactions play a crucial role in controlling the molecular arrangements in the resulting assemblies. This research will open new insights into exploring controllable molecular motions and assemblies in the solid state, providing new perspectives in supramolecular chemistry and materials.

Guest-induced amorphous-to-crystalline transformation enables sorting of haloalkane isomers with near-perfect selectivity

“…Selective removal of two hydroxy or alkoxy groups on one subunit of traditional P[ n ]As turns out to be much more unachievable because of the extreme difficulty to precisely crack two aryl-O bonds on one alkoxybenzene subunit. Previously, we discovered that the critical step for MeP[5]L synthesis is the initial construction of two kinds of coupling precursors ( 40 ). Accordingly, in this research, we successfully synthesized per-hydroxylated P[5]L ( P[5]L ), perethylated P[5]L ( EtP[5]L ), perethylated P[6]L ( EtP[6]L ), BrP[5]L , and two other important functional derivatives P[5]L-1 and P[5]L-2.…”

“…Selective removal of two hydroxy or alkoxy groups on one subunit of traditional P[n]As turns out to be much more unachievable because of the extreme difficulty to precisely crack two aryl-O bonds on one alkoxybenzene subunit. Previously, we discovered that the critical step for MeP [5]L synthesis is the initial construction of two kinds of coupling precursors (40). Accordingly, in this research, we successfully synthesized per-hydroxylated P [5] 13 C nuclear magnetic resonance (NMR) spectroscopies, matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry (MALDI-TOF MS) spectroscopy, and density functional theory (DFT) analysis (Fig.…”

“…Pillararenes, a new generation of supramolecular hosts, have been classified as one of the most iconic macrocyclic containers among the well-established ones (e.g., crown ethers, cyclodextrins, cucurbiturils, and calixarenes) (37)(38)(39) and gained tremendous momentum during the modern supramolecular chemistry boom. Recently, we have presented an example of pillar [5]arene-derived macrocyclic receptor, named permethylated leggero pillar [5]arene (MeP [5]L) (40), in which two methoxy functionalities on a single one of the subunits of traditional permethylated pillar [5]arene were selectively removed. We also found that the amorphous powder of MeP [5]L can physically adsorb certain types of guest vapors accompanied by the molecular packing transition from the initially chaotic state to various ordered states.…”

A Pd2L4 Metallacage‐Cored Supramolecular Amphiphile and Its Application in Dual‐Responsive Controllable Release†

“…[ 28‐30 ] Unlike covalent‐bond based amphiphiles, supramolecular amphiphiles [ 31‐32 ] are constructed by noncovalent interactions including host–guest interactions, π–π stacking, metal coordination and hydrogen bonding. [ 33‐43 ] Compared with traditional amphiphiles, the advantage of supramolecular amphiphiles is that the functional groups can be combined under mild conditions, which can effectively avoid multiple complicated steps and purification processes in the synthesis of amphiphiles. [ 44‐45 ] More importantly, due to the dynamic and reversible nature of noncovalent interactions, self‐assembly systems constructed by supramolecular amphiphiles are tunable and exhibit responsiveness to external stimuli, [ 46‐48 ] making them of outstanding value in drug delivery, protein probes, nanodevices and other fields.…”

Separation of pyrrolidine from tetrahydrofuran by using pillar[6]arene-based nonporous adaptive crystals

“…In the past decade, pillararenes have been widely studied in supramolecular chemistry. 9 Owing to their unique pillar structures and diverse host–guest recognitions, pillararenes have been used in the construction of numerous supramolecular systems. 10 Recently, nonporous adaptive crystals (NACs) of macrocycles, which have shown extraordinary performance in adsorption and separation, have been developed by our group as a new type of adsorption and separation materials.…”