All-Carbon-Linked Continuous Three-Dimensional Porous Aromatic Framework Films with Nanometer-Precise Controllable Thickness

[Image: see text] Inherently porous materials that are chemically and structurally robust are challenging to construct. Conventionally, dynamic chemistry is thought to be needed for the formation of uniform porous organic frameworks, but dynamic bonds can limit the stability of these materials. For this reason, all-carbon-linked frameworks are expected to exhibit higher stability performance than more traditional porous frameworks. However, the limited reversibility of carbon–carbon bond-forming reactions has restricted the exploration of these materials. In particular, the challenges associated with producing uniform thin films of all-carbon-linked frameworks has inhibited the study of these materials in applications where well-defined films are required. Here, we synthesize continuous and homogeneous films of two different all-carbon-linked three-dimensional porous aromatic frameworks with nanometer-precision thickness (PAF-1 and BCMP-2). This was accomplished by kinetically promoting surface reactivity while suppressing homogeneous nucleation. Through connection of the PAF film to a gold substrate via a self-assembled monolayer and use of flow conditions to continually introduce monomers, smooth and continuous PAF films can be grown with controlled thickness. This strategy allows traditional transition metal mediated carbon–carbon cross-coupling reactions to form porous, organic thin films. We expect that the chemical principles uncovered in this study will enable the synthesis of a variety of chemically and structurally diverse carbon–carbon-linked frameworks as high-quality films, which are inaccessible by conventional methods.