Discrete Giant Polymeric Chains Based on Nanosized Monomers

[Image: see text] As size-amplified analogues of canonical macromolecules, polymeric chains built up by “giant” monomers represent an experimental realization of the “beads-on-a-string” model at larger length scales, which could provide insights into fundamental principles of polymer science. In this work, we modularly constructed discrete giant polymeric chains using nanosized building blocks (polyhedral oligomeric silsesquioxane, POSS) as basic repeat units through an efficient and robust iterative exponential growth approach, with precise control on molecular parameters, including size, composition, regioconfiguration, and surface functionalities. Their chemical structures were fully characterized by nuclear magnetic resonance spectroscopy, size-exclusion chromatography, and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. With elaborately designed amphiphilic block POSS chains and their analogues made of conventional monomers, the size effects were delicately studied and highlighted. Interesting assembly behaviors emerge as a result of distinct interactions and molecular dynamics. This category of molecules shares general self-assembly characteristics as the conventional counterparts in terms of phase transition and evolution. Meanwhile, it turns out that the monomer size has profound impacts on phase stability, as a trade-off between entropic and enthalpic contributions. It may open up a door for modular and programmable design of interesting materials with complex structures and diverse functions.