Complex multiscale assemblies of metal–organic frameworks are essential in the construction of large-scale optical platforms but often restricted by their bulk nature and conventional techniques. The integration of nanomaterials and 3D printing technologies allows the fabrication of multiscale functional architectures. Our study reports a unique method of controlled 3D assembly purely relying on the post-printing treatment of printed constructs. By immersing a 3D-printed patterned construct consisting of organic ligand in a solution of lanthanide ions, in situ growth of lanthanide metal–organic frameworks (LnMOFs) can rapidly occur, resulting in macroscopic assemblies and tunable fluorescence properties. This phenomenon, caused by coordination and chelation of lanthanide ions, also renders a sub-millimeter resolution and high shape fidelity. As a proof of concept, a type of 3D assembled LnMOFs-based optical sensing platform has demonstrated the feasibility in response to small molecules such as acetone. It is anticipated that the facile printing and design approach developed in this work can be applied to fabricate bespoke multiscale architectures of functional materials with controlled assembly, bringing a realistic and economic prospect.

金属有机框架的复杂多尺度组装在大型光学平台的构建中是必不可少的，但通常受到其体积性质和传统技术的限制。纳米材料和 3D 打印技术的集成允许制造多尺度功能架构。我们的研究报告了一种独特的受控 3D 组装方法，完全依赖于打印结构的打印后处理。通过将由有机配体组成的 3D 打印图案化结构浸入镧系离子溶液中，镧系金属-有机框架 (LnMOF) 可以快速原位生长，从而实现宏观组装和可调荧光特性。这种由镧系离子的配位和螯合引起的现象也呈现亚毫米分辨率和高形状保真度。作为概念验证，一种基于 3D 组装 LnMOFs 的光学传感平台已经证明了响应丙酮等小分子的可行性。预计这项工作中开发的简便印刷和设计方法可用于制造具有可控组装的功能材料的定制多尺度结构，带来现实和经济的前景。