Stabilization of Supramolecular Nanostructures Induced by Self-Assembly of Dendritic Building Blocks

Abstract

Dendrons with amide-urethane branch units and topochemically polymerizable diacetylene moieties at the alkyl periphery were synthesized via a convergent method. They form organized nanostructures in organic media and also in water. In organic media, they form lamella or columnar hexagonal structures depending on the dendron generation. By changing the solvent from organic to aqueous phase, the identical dendritic building blocks self-organize into a vesicular structure. The noncovalent interactions such as hydrogen bonding of the dendritic branches and van der Waals interactions of the alkyl periphery are critical for the construction of organized structures. These supramolecular nanostructures induced via selfassembly of dendritic building blocks could remarkably be stabilized by in situ photopolymerization of topochemically polymerizable diacetylene moieties incorporated at the periphery of the dendrons in organized states.

Electrochemical behavior on poly(ferrocenyldimethylsilane)-b-poly(benzyl ether) linear-dendritic organometallic polymer films

“…All synthesized poly(ferrocenophane)s exhibit electrochemical activity, and poly(ferrocenophane)s with different structures show distinguished cyclic voltammetry behavior [17][18][19][20], which will help us understand the relationship between structure, property and charge transfer mechanism, and benefit to design different functional modified electrodes. Dendritic molecules present a number of new possibilities in the areas of molecular engineering and nanotechnology due to their unique dendritic structure [21][22][23][24][25][26][27][28]. Thus, by incorporating dendritic molecules into poly(ferrocenylsilane)s polymer systems, one can potentially design a variety of functional organometallic polymer materials.…”

Self-assembly using dendritic building blocks—towards controllable nanomaterials

“…In an extension of this work, alkyne functionalities were incorporated into the long hydrophobic tails on the periphery of the dendritic structure [131]. TEM images of the second generation dendron indicated the presence of fibrous bundles, and X-ray diffraction (XRD) of the dried gels indicated that these fibres had a hexagonal columnar structure.…”

Dendritic Gels—Many Arms Make Light Work

“…This type of 'covalent capture' strategy has been widely applied in dendrimer chemistry by Zimmerman and co-workers [21] and has been extended to the field of dendritic gels by our group, as well as that of Kim. [22] Dendritic surfaces are ideal for the covalent capture of nanoscale architectures because the multiplicity of the surface groups gives rise to a better chance of effective crosslinking. Clearly this strategy is somewhat similar to Grinstaff's use of peripheral polymerizable groups for the formation of crosslinked gels described above.…”

“…Using this type of approach, Kim et al reported a dendritic gelator that has bis-alkyne groups on the periphery. [22] These groups undergo photoinitiated crosslinking when in close proximity to one another. Kim et al demonstrated that photoirradiation of their gels led to crosslinking of the gelphase material.…”