An Accelerated Modular-Orthogonal Ni-Catalyzed Methodology to Symmetric and Nonsymmetric Constitutional Isomeric AB₂ to AB₉ Dendrons Exhibiting Unprecedented Self-Organizing Principles

Abstract

Five libraries of natural and synthetic phenolic acids containing five AB3, ten constitutional isomeric AB2, one AB4, and one AB5 were previously synthesized and reported by our laboratory in 5 to 11 steps. They were employed to construct seven libraries of self-assembling dendrons, by divergent generational, deconstruction, and combined approaches, enabling the discovery of a diversity of supramolecular assemblies including Frank–Kasper phases, soft quasicrystals, and complex helical organizations, some undergoing deracemization in the crystal state. However, higher substitution patterns within a single dendron were not accessible. Here we report three libraries consisting of 30 symmetric and nonsymmetric constitutional isomeric phenolic acids with unprecedented sequenced patterns, including two AB2, three AB3, eight AB4, five AB5, six AB6, three AB7, two AB8, and one AB9 synthesized by accelerated modular-orthogonal Ni-catalyzed borylation and cross-coupling. A single etherification step with 4-(n-dodecyloxy)­benzyl chloride transformed all these phenolic acids, of interest also for other applications, into self-assembling dendrons. Despite this synthetic simplicity, they led to a diversity of unprecedented self-organizing principles: lamellar structures of interest for biological membrane mimics, helical columnar assemblies from rigid-solid angle dendrons forming Tobacco Mosaic Virus-like assemblies, columnar organizations from adaptable-solid angle dendrons forming disordered micellar-like nonhelical columns, columns from supramolecular spheres, five body-centered cubic phases displaying supramolecular orientational memory, rarely encountered in previous libraries forming predominantly Frank–Kasper phases, and two Frank–Kasper phases. Lessons from these self-organizing principles, discovered within a single generation of self-assembling dendrons, may help elaborate design principles for complex helical and nonhelical organizations of synthetic and biological matter.

Supramolecular Proton Conductors Self-Assembled by Organic Cages

“…The pendant hydroxyl group(s) on Cage-1 and -2 was introduced for solubility and easy solution processibility. As the molecular packing of supramolecular structures and their functions are determined by the self-assembling synthons, − we reasoned that the self-assembly of the two cages would yield two different supramolecular proton conductors with distinct intermolecular channels, which might alter the proton conduction behaviors of the encapsulated proton carriers.…”

From Frank–Kasper, Quasicrystals, and Biological Membrane Mimics to Reprogramming In Vivo the Living Factory to Target the Delivery of mRNA with One-Component Amphiphilic Janus Dendrimers

“…A few polyphenols and the three most commonly used plant phenolic acids employed in our laboratory are outlined in Figure . Thirty new symmetric and nonsymmetric phenolic acids were synthesized from the compounds illustrated in Figure . − This was possible only after Pd was replaced with the more reactive but less expensive Ni in the borylation and cross-coupling catalytic cycles. − The transition from Pd to Ni started in 1995 in our laboratory, ,− continued with the development of more reactive and more stable sigma Ni complexes, the mixed-ligand concept, and other strategies that are part of previous large review articles. , Therefore, only the most recent accomplishments are cited here. ,, Thio-bromo “click” − and other click reactions also had an important impact as synthetic methodologies employed with phenolic acids or with other renewable reagents. However, the discovery of the mixed-ligand and catalytic effect of solvent in single-electron transfer living radical polymerization (SET-LRP). ,,− has not yet impacted at the same level the field of self-organizable helical columnar and spherical helical dendronized polymers.…”

Supramolecular assembly of dendronized spiropyrans in aqueous solutions into nanospheres with photo- and thermo-responsive chiralities

“…[1][2][3] The major structural characteristics of dendritic macromolecules include their monodispersity, nonlinear topology and multivalency, which make a big difference compared to conventional polydisperse polymers in assemblies and their assembled morphology control. 3 Non-linear topological structures from dendritic macromolecules afford the molecular segments different packing parameters, resulting in abundant ordered phases in bulk 2,[4][5][6] or in solutions. 7,8 Multivalency from dendritic macro-molecules is important in manipulating the assembly, especially when associations play pivotal roles in controlling morphologies of the assemblies.…”