Two-dimensional calix[4]arene-based metal-organic coordination networks of tunable crystallinity

We present a flexible and versatile method to fabricate two-dimensional metal-organic coordination networks (MOCNs) by bottom-up self-assembly. 2D crystalline layers are formed at the air-water interface, coordinated by ions from the liquid phase and transferred onto a solid substrate with their crystallinity preserved. By using an inherently three-dimensional amphiphile, namely 5,11,17,23-tetra-carboxy-25,26,27,28 tetrapropoxycalix[4]arene (1), and a copper metal node; large and mono-crystalline dendritic MOCN domains were formed. The method described herein allows for the fabrication of monolayers of tunable crystallinity on liquid and solid substrates. It can be applied to a large range of differently functionalized organic building blocks, also beyond macrocycles and can be interconnected by diverse metal nodes.