Coassembly of a Hexagonal Columnar Liquid Crystalline Superlattice from Polymer(s) Coated with a Three-Cylindrical Bundle Supramolecular Dendrimer

Abstract

Abstract:The synthesis and structural analysis of a polymer containing twindendritic benzamide side-groups (i.e. poly{N-[3,4-bis(n-dodecan-1-yloxy)-5-(1-methacryloyl-n-undecan-1-yloxy)-phenyl]-3,4,5-tris(n-dodecan-1-yloxy)-benzamide}) (19) are described. The disc-like side groups of this polymer self-assemble into supramolecular cylindrical dendrimers through hydrogen bonding acting along the column long axis, creating a novel architecture consisting of a polymer chain(s) coated with a three-cylindrical bundle supramolecular dendrimer. This polymer self-organizes in a thermotropic nematic liquid crystalline (LC) phase. The low molar mass twin dendritic benzamide, 7-12/12, which has a similar structure to that of the polymer side groups, self-assembles into supramolecular cylindrical dendrimers, which self-organize on a twodimensional hexagonal columnar (F h ) LC lattice. Coassembly of the polymer 19 with 7-12/12 produces a novel twodimensional F h LC superlattice. The mechanism responsible for this coassembly provides access to libraries of functional two-dimensionl F h superlattices.

Self-assembly of amphiphilic Janus dendrimers into uniform onion-like dendrimersomes with predictable size and number of bilayers

“…This report will demonstrate the synthetic capabilities of first-generation dendrons, denoted previously as minidendrons (41), as models or maquettes for the discovery of novel architectural motifs that may be accessible also from higher generations of Janus dendrimers during self-assembly in water. The role of these minidendrons (41)(42)(43) and Janus minidendrimers is analogous to that of simple peptides used in the understanding of molecular engineering involved during the assembly of more complex proteins, or of maquettes used by sculptors and architects to appreciate various aspects of full-size objects (41,44). The minidendron concept has been already demonstrated to be successful for the discovery of a variety of novel complex architectures and functions (41,43), the most recent example being in the discovery of supramolecular homochirality by chiral self-sorting during supramolecular helical organization (42).…”

Effect of Structural Parameters on the Supramolecular Organization of Rigid‐Flexible Polymers

“…Subsequently, the organizational features of such multi-alkoxy substituted dendrons were successfully used through the polymerization of various such vinylic macromonomers towards the development of new macromolecular objects of well-defined, predictable shapes. [9][10][11][12][13][14][15][16] In general, an intense scientific effort has been devoted towards the syntheses and conformational characterization of various dendronized polymers. [17][18][19] Also natural amphiphilic dendritic dipeptides have recently been reported which self-assemble in solution and in bulk through a complex recognition process into helical pores.…”

Plastic- and liquid-crystalline architectures from dendritic receptor molecules

“…At a cooling rate of 10°C min Ϫ1 , 2 does not return to a crystalline state, but rather cools to an amorphous solid, without evidence of an exotherm in the DSC thermogram that corresponds to a crystallization event. At a low cooling rate, the crystallization exotherm is present, but the large degree of supercooling (Ͼ60°C) of the transition is evidence of the difficult ordering (35). Similar difficulties in crystallization have been observed for related tapered monodendritic compounds (35,36).…”

“…At a low cooling rate, the crystallization exotherm is present, but the large degree of supercooling (Ͼ60°C) of the transition is evidence of the difficult ordering (35). Similar difficulties in crystallization have been observed for related tapered monodendritic compounds (35,36). It has been rationalized that the presence of the alkyl chains, and in particular the meta-substituted ones, in combination with the high molecular weight of the compounds makes it difficult for the molecules to return to the crystalline state without extensive annealing.…”