4 research outputs found
Dimerization Control in the Self-Assembly Behavior of Copillar[5]arenes Bearing ω‑Hydroxyalkoxy Groups
Two novel copillar[5]Âarenes bearing ω-hydroxyalkoxy
groups
are synthesized and their self-assembly properties are studied by <sup>1</sup>H NMR spectroscopy, specific viscosity, and X-ray measurements.
The copillar[5]Âarene <b>2b</b> bearing a 6-hydroxyhexyloxy group
exhibits a reversible self-assembly behavior, leading to the formation
of the self-inclusion monomer and hugging dimers. The reversible self-assembly
behavior can be controlled by tuning solvent, temperature, guest,
and H-bond interaction. However, the copillar[5]Âarene <b>2a</b> bearing a short 4-hydroxybutyloxy group does not show such a self-assembly
behavior to the formation of the self-inclusion monomer and hugging
dimers
Dimerization Control in the Self-Assembly Behavior of Copillar[5]arenes Bearing ω‑Hydroxyalkoxy Groups
Two novel copillar[5]Âarenes bearing ω-hydroxyalkoxy
groups
are synthesized and their self-assembly properties are studied by <sup>1</sup>H NMR spectroscopy, specific viscosity, and X-ray measurements.
The copillar[5]Âarene <b>2b</b> bearing a 6-hydroxyhexyloxy group
exhibits a reversible self-assembly behavior, leading to the formation
of the self-inclusion monomer and hugging dimers. The reversible self-assembly
behavior can be controlled by tuning solvent, temperature, guest,
and H-bond interaction. However, the copillar[5]Âarene <b>2a</b> bearing a short 4-hydroxybutyloxy group does not show such a self-assembly
behavior to the formation of the self-inclusion monomer and hugging
dimers
Supramolecular Polymer Polymorphism: Spontaneous Helix–Helicoid Transition through Dislocation of Hydrogen-Bonded π‑Rosettes
Polymorphism, a phenomenon whereby disparate self-assembled
products
can be formed from identical molecules, has incited interest in the
field of supramolecular polymers. Conventionally, the monomers that
constitute supramolecular polymers are engineered to facilitate one-dimensional
aggregation and, consequently, their polymorphism surfaces primarily
when the states of assembly differ significantly. This engenders polymorphs
of divergent dimensionalities such as one- and two-dimensional aggregates.
Notwithstanding, realizing supramolecular polymer polymorphism, wherein
polymorphs maintain one-dimensional aggregation, persists as a daunting
challenge. In this work, we expound upon the manifestation of two supramolecular polymer polymorphs formed from a large discotic
supramolecular monomer (rosette), which consists of six hydrogen-bonded
molecules with an extended π-conjugated core. These polymorphs
are generated in mixtures of chloroform and methylcyclohexane, attributable
to distinctly different disc stacking arrangements. The face-to-face
(minimal displacement) and offset (large displacement) stacking arrangements
can be predicated on their distinctive photophysical properties. The
face-to-face stacking results in a twisted helix structure. Conversely,
the offset stacking induces inherent curvature in the supramolecular
fiber, thereby culminating in a hollow helical coil (helicoid). While
both polymorphs exhibit bistability in nonpolar solvent compositions,
the face-to-face stacking attains stability purely in a kinetic sense
within a polar solvent composition and undergoes conversion into offset
stacking through a dislocation of stacked rosettes. This occurs without
the dissociation and nucleation of monomers, leading to unprecedented
helicoidal folding of supramolecular polymers. Our findings augment
our understanding of supramolecular polymer polymorphism, but they
also highlight a distinctive method for achieving helicoidal folding
in supramolecular polymers
Supramolecular Polymer Polymorphism: Spontaneous Helix–Helicoid Transition through Dislocation of Hydrogen-Bonded π‑Rosettes
Polymorphism, a phenomenon whereby disparate self-assembled
products
can be formed from identical molecules, has incited interest in the
field of supramolecular polymers. Conventionally, the monomers that
constitute supramolecular polymers are engineered to facilitate one-dimensional
aggregation and, consequently, their polymorphism surfaces primarily
when the states of assembly differ significantly. This engenders polymorphs
of divergent dimensionalities such as one- and two-dimensional aggregates.
Notwithstanding, realizing supramolecular polymer polymorphism, wherein
polymorphs maintain one-dimensional aggregation, persists as a daunting
challenge. In this work, we expound upon the manifestation of two supramolecular polymer polymorphs formed from a large discotic
supramolecular monomer (rosette), which consists of six hydrogen-bonded
molecules with an extended π-conjugated core. These polymorphs
are generated in mixtures of chloroform and methylcyclohexane, attributable
to distinctly different disc stacking arrangements. The face-to-face
(minimal displacement) and offset (large displacement) stacking arrangements
can be predicated on their distinctive photophysical properties. The
face-to-face stacking results in a twisted helix structure. Conversely,
the offset stacking induces inherent curvature in the supramolecular
fiber, thereby culminating in a hollow helical coil (helicoid). While
both polymorphs exhibit bistability in nonpolar solvent compositions,
the face-to-face stacking attains stability purely in a kinetic sense
within a polar solvent composition and undergoes conversion into offset
stacking through a dislocation of stacked rosettes. This occurs without
the dissociation and nucleation of monomers, leading to unprecedented
helicoidal folding of supramolecular polymers. Our findings augment
our understanding of supramolecular polymer polymorphism, but they
also highlight a distinctive method for achieving helicoidal folding
in supramolecular polymers