This work describes the first rigorous example of a single-component block copolymer system forming unconventional spherical phases. A library of discrete block polymers with uniform chain length and diverse architectures were modularly prepared through a combination of a step-growth approach and highly efficient coupling reactions. The precise chemical structure eliminates all the molecular defects associated with molar weight, dispersity, and compositional ratio. Complex spherical phases, including the Frank–Kasper phase (A15 and σ) and quasicrystalline phase, were experimentally captured by meticulously tuning the composition and architectures. A phase portrait with unprecedented accuracy was mapped out (up to one monomer resolution), unraveling intriguing details of phase behaviors that have long been compromised by inherent molecular weight distribution. This study serves as a delicate model system to bridge the existing gaps between experimental observations and theoretical assessments and to provide insights into the formation and evolution of the unconventional spherical phases in soft matter systems.

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.

Molecular shape is an essential parameter that regulates the self-organization and recognition process, which has not yet been well appreciated and exploited in block polymers due to the lack of precise and efficient modulation methods. This work (i) develops a robust approach to break the intrinsic symmetry of linear polymers by introducing geometric features into otherwise homo­geneous chains and (ii) quantitatively highlights the critical contribution of molecular geometry/architecture to the self-assembly behaviors. Iteratively connecting homologous monomers of different side chains according to pre-designed sequences generates discrete polymers with exact chemical structure, uniform chain length, and programmable side-chain gradient along the backbone, which transcribes into diverse shapes. The precise chemistry eliminates all the defects and heterogeneities, providing a delicate platform for fundamental inquiries into the role of molecular geometry. A rich collection of unconventional complex phases, including Frank–Kasper A15 and σ phases, as well as a dodecagonal quasicrystal phase, were captured in these rigorous single-component systems. The self-assembly behaviors are strikingly sensitive to subtle variations of geometry, such that simply migrating a few methylene units among the side chains would generate substantial differences in lattice size or phase stability, or even trigger a phase transition toward distinct structures. The phenomena can be rationalized with a geometric argument that nonuniform side chain distribution leads to conformational mismatch between two immiscible blocks, resulting in varied interfacial curvatures and distinct lattice symmetries. The profound contribution demonstrates that molecular geometry is an effective and robust parameter for structural engineering.

Conformational asymmetry of block copolymers is a critical molecular parameter dictating the self-assembly behaviors. This work develops an efficient approach to construct block copolymers with uniform chain length and tunable conformational mismatch. Three model discrete diblock copolymers based on γ-alkyl-α-hydroxy glutaric acid and lactide monomers were prepared through the iterative growth approach. The conformational asymmetry can be adjusted via simple substitution of the hydrocarbon side chains. The precise chemical structure rules out all molecular uncertainties associated with statistical distribution, providing a delicate platform for quantitatively resolving the intricate details and underlying principles. Diverse ordered structures, including the Frank–Kasper σ and A15 phases and quasicrystalline phase, were captured. A phase portrait with an exceptionally high compositional resolution was mapped, demonstrating clearly that the spherical packing region expands and the complex phases emerge as the conformational asymmetry increases. This study explicitly correlates the origin of the intriguing structures with the intrinsic molecular parameters, providing deep insights into the formation and evolution of the complex phases in block copolymers.

Polymeric chains made of "giant" monomers at a larger length scale provide intriguing insights into the fundamental principles of polymer science. In this study, we modularly prepared a library of discrete amphiphilic polymeric chains using molecular nanoparticles as repeat units, with exact control of composition, chain length, surface property, and regio-configuration. These giant polymeric chains selfassembled into a rich collection of highly ordered phases. The precise chemical structure and uniform chain length eliminate all the inherent molecular "defects", while the nanosized monomer amplifies minute structural differences, providing an ideal platform for a systematic scrutiny of the self-assembly behaviors at a larger length scale. The compositional and regioconfigurational contribution was carefully studied. The regio-regularity is found to have a direct and profound impact on the chain conformation, leading to a distinct molecular packing scheme and therefore shifting the phase boundaries. With increasing the length of the linker, the regio-constraint gradually diminishes, and the neighboring particles would eventually be decoupled.