Manipulating the Self‐Assembly of Multicomponent Low Molecular Weight Gelators (LMWGs) through Molecular Design

Multicomponent low molecular weight gelators (LMWGs) may self‐assemble by co‐assembly (CA), social self‐sorting (SSS), or narcissistic self‐sorting (NSS). Understanding the nuances of the self‐assembly processes is important to predict the behavior of multicomponent organogels. Here, we investigate the effect of molecular structure on self‐assembly in a series of amino‐acid based bicomponent LMWGs that differ in headgroup and alkyl chain length. Packing preference of the organogels was determined using differential scanning calorimetry, nuclear magnetic resonance spectroscopy and small angle X‐ray scattering. From 66 bicomponent samples we found 50 CA, 14 SSS and 2 NSS. Furthermore, we performed statistical analysis to investigate the role of hydrophobicity and chain length on the overall pathway of self‐assembly for these systems. We found the hydrophobicity of the headgroup strongly affected the assembly preference of the organogel, but alkyl chain length only played a small role. Design principles for a series of organogels through statistical analysis were established by synthesizing a library of compounds and analyzing their properties. This approach predicts the self‐assembly and gelation concentration through the molecular design of the gelator building blocks.