Synthesis of Two-Dimensional Analogues of Copolymers by Site-to-Site Transmetalation of Organometallic Monolayer Sheets

Monolayer sheets have gained attention due to the unique properties derived from their two-dimensional structure. One of the key challenges in sheet modification/synthesis is to exchange integral parts while keeping them intact. We describe site-to-site transmetalation of Zn2+ in the netpoints of cm2-sized, metal–organic sheets by Fe2+, Co2+, and Pb2+. This novel transformation was done both randomly and at predetermined patterns defined by photolithography to create monolayer sheets composed of different netpoints. All transmetalated sheets are mechanically strong enough to be spanned over 20 × 20 μm2 sized holes. Density functional theory calculations provide both a model for the molecular structure of an Fe2+-based sheet and first insights into how transmetalation proceeds. Such transmetalated sheets with random and patterned netpoints can be considered as two-dimensional analogues of linear copolymers. Their nanoscale synthesis presents an advance in monolayer/polymer chemistry with applications in fields such as surface coating, molecular electronics, device fabrication, imaging, and sensing.