Exploring and Expanding the Structural Diversity of Self‐Assembling Dendrons through Combinations of AB, Constitutional Isomeric AB 2 , and AB 3 Biphenyl‐4‐Methyl Ether Building Blocks

General, efficient and inexpensive methods for the synthesis of dendritic building blocks methyl 3′,4′‐dihydroxybiphenyl‐4‐carboxylate, 3′,5′‐dihydroxybiphenyl‐4‐carboxylate, and methyl 3′,4′,5′‐trihydroxybiphenyl‐4‐carboxylate were elaborated. In all syntheses the major step involved an inexpensive Ni II ‐catalyzed Suzuki cross‐coupling reaction. These three building blocks were employed together with methyl 4′‐hydroxybiphenyl‐4‐carboxylate in a convergent iterative strategy to synthesize seven libraries containing up to three generations of 3′,4′‐, 3′,5′‐, and 3′,4′,5′‐substituted biphenyl‐4‐methyl ether based amphiphilic dendrons. These dendrons self‐assemble into supramolecular dendrimers that self‐organize into periodic assemblies. Structural and retrostructural analysis of their assemblies demonstrated that these dendrons self‐assemble into hollow and non‐hollow supramolecular dendrimers exhibiting dimensions of up to twice those reported for architecturally related dendrons based on benzyl ether repeat units. These new dendrons expand the structural diversity and demonstrate the generality of the concept of self‐assembling dendrons based on amphiphilic arylmethyl ethers.