The three-dimensional arrangement of natural and synthetic network materials determines their application range. Control over the real-time incorporation of each building block and functional group is desired to regulate the macroscopic properties of the material from the molecular level onwards. Here we report an approach combining kinetic Monte Carlo and molecular dynamics simulations that chemically and physically predicts the interactions between building blocks in time and in space for the entire formation process of three-dimensional networks. This framework takes into account variations in inter- and intramolecular chemical reactivity, diffusivity, segmental compositions, branch/network point locations and defects. From the kinetic and three-dimensional structural information gathered, we construct structure–property relationships based on molecular descriptors such as pore size or dangling chain distribution and differentiate ideal from non-ideal structural elements. We validate such relationships by synthesizing organosilica, epoxy–amine and Diels–Alder networks with tailored properties and functions, further demonstrating the broad applicability of the platform.

天然和合成网络材料的三维排列决定了它们的应用范围。需要控制每个构建块和官能团的实时结合，以从分子水平开始调节材料的宏观性质。在这里，我们报告了一种结合动力学蒙特卡罗和分子动力学模拟的方法，该方法在化学和物理上预测了三维网络整个形成过程中构建块之间在时间和空间上的相互作用。该框架考虑了分子间和分子内化学反应性、扩散率、链段组成、分支/网络点位置和缺陷的变化。从收集到的动力学和三维结构信息中，我们根据孔径或悬链分布等分子描述符构建结构-性质关系，并将理想结构元素与非理想结构元素区分开来。我们通过合成具有定制属性和功能的有机二氧化硅、环氧胺和狄尔斯-桤木网络来验证这种关系，进一步证明了该平台的广泛适用性。