A hidden chemical assembly mechanism: reconstruction‐by‐reconstruction cycle growth in HKUST‐1 MOF layer synthesis

Thin metal‐organic framework films grown in a layer‐by‐layer manner have been the subject of growing interest. Herein we investigate one of the most popular frameworks, the type HKUST‐1. Firstly, we show a special synthesis procedure resulting in quick but optically perfect growth. This enables the synthesis of films of excellent optical quality within a short timeframe. Secondly and most importantly, we address the known, but not fully understood observation that the expected growth rate of one monolayer per cycle is strongly exceeded, e.g. by a factor of 4. This is an often‐ignored inconsistency in the literature. We offer a growth model using a reconstruction process in every cycle leading to a deterministic reconstruction‐by‐reconstruction (RbR) cycle growth with a 4‐times higher growth rate. It represents an up‐to‐now hidden chemical assembly mechanism.