Date of Award


Degree Type


Degree Name

Doctor of Philosophy (PhD)

Graduate Group


First Advisor

David W. Christianson



ADVANCES IN SUPRAMOLECULAR ORIENTATIONAL MEMORY MEDIATED BY FRANK-KASPER PHASES OF SELF-ASSEMBLING DENDRONSNing Huang Virgil Percec Synthetic methodologies to develop and program complex self-assembling soft matter have pushed the forefront of bioinspired materials, nanoscale architecture design, and the development of drug delivery systems. Self-assembling dendrons and dendrimers have emerged as one of the most promising candidates that allow monodisperse molecular weights, programmable primary structures, sequence-defined peripheral groups, and versatile functional group modifications. To control the functions of supramolecular assemblies in complex biological and non-biological systems, it is necessary to define and program their structures via the molecular design of self-assembling dendrons. In this work, three novel synthetic strategies are introduced to the field of soft matter design. These include: an accelerated, nickel-catalyzed cross-coupling methodology to synthesize symmetric and nonsymmetric self-assembling dendrons; a sequence-defined synthetic method to facilitate highly ordered self-organization in the solid state; and a new class of drug delivery vesicles self-assembled from ionizable amphiphilic Janus dendrimers. Structural and retrostructural analyses are conducted by a robust methodology that includes: initial investigation of thermal behavior of supramolecular assemblies by differential scanning calorimetry; structural determination of supramolecular assemblies by oriented fiber X-ray diffraction (XRD); mechanistic studies supported by molecular modeling; and XRD simulation of the constructed models of supramolecular assemblies. The scientific findings reported in this work consist of: (1) an accelerated synthetic route to obtain self-assembling dendrons with rigid solid angle; (2) statistical and mechanistic studies of supramolecular orientational memory (SOM); (3) the development of SOM-competent noncovalent crown conformations via the tuning of intermolecular interactions at the apex of a self-assembling dendron; (4) the discovery of two unprecedented arrangements of columnar hexagonal lattices; (5) a sequence-defined modification on the peripheral groups of a self-assembling dendron that drastically enhances the self-organization of its supramolecular assemblies; and (6) a sequence-defined ionizable amphiphilic Janus dendrimer employed in mRNA delivery systems. In conclusion, the principles of supramolecular self-assembly and the newly developed synthetic methodologies elaborated in this work are expected to facilitate advances in the design and synthesis of functional supramolecular materials.

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