Atoms serve as an inspiration for colloidal self-assembly, whereby building blocks can combine and confer endless functionality using a few design principles, including directionality, valence and reversible binding. Tetrahedral structures inspired by the bonding of carbon atoms have long been targeted as candidates for metamaterials and are now becoming accessible through molecular mimetic colloidal building blocks. Beyond carbon mimics, increasingly complex particles are being synthesized that can be arranged in their own periodic table and used to generate forms of matter unique to colloidal systems. This Review presents a framework to describe the synthesis of these micrometre-scale colloids, in which the fundamental constituents are either combined through interparticle reactions or transformed through intraparticle reactions, in analogy to molecules in traditional synthetic chemistry. We build on this framework to illustrate how unique particle shape and surface chemistry leads to diverse assembly routes for these colloidal building blocks.

原子是胶体自组装的灵感来源，由此构建块可以使用一些设计原则（包括方向性、价态和可逆结合）组合并赋予无穷无尽的功能。受碳原子键合启发的四面体结构长期以来一直被视为超材料的候选者，现在可以通过分子模拟胶体构建块获得。除了碳模拟物之外，正在合成越来越复杂的粒子，这些粒子可以排列在它们自己的元素周期表中，并用于生成胶体系统特有的物质形式。本综述提出了一个框架来描述这些微米级胶体的合成，其中基本成分要么通过粒子间反应结合，要么通过粒子内反应转化，类似于传统合成化学中的分子。我们以此框架为基础来说明独特的颗粒形状和表面化学如何导致这些胶体构建块的不同组装路线。