title: Synthesis of two-dimensional analogues of copolymers by site-to-site transmetalation of organometallic monolayer sheets.
abstract: 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 Zn(2+) in the netpoints of cm(2)-sized, metal-organic sheets by Fe(2+), Co(2+), and Pb(2+). 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 μm(2) sized holes. Density functional theory calculations provide both a model for the molecular structure of an Fe(2+)-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.
authors.affiliation: Laboratory of Polymer Chemistry, Institute of Polymers, Department of Materials, ETH Zürich , Vladimir-Prelog-Weg 5, CH-8093 Zürich, Switzerland.
authors.forename: Zhikun
authors.initials: Z
authors.lastname: Zheng
authors.forename: Lothar
authors.initials: L
authors.lastname: Opilik
authors.forename: Florian
authors.initials: F
authors.lastname: Schiffmann
authors.forename: Wei
authors.initials: W
authors.lastname: Liu
authors.forename: Giacomo
authors.initials: G
authors.lastname: Bergamini
authors.forename: Paola
authors.initials: P
authors.lastname: Ceroni
authors.forename: Lay-Theng
authors.initials: LT
authors.lastname: Lee
authors.forename: Andri
authors.initials: A
authors.lastname: Schütz
authors.forename: Junji
authors.initials: J
authors.lastname: Sakamoto
authors.forename: Renato
authors.initials: R
authors.lastname: Zenobi
authors.forename: Joost
authors.initials: J
authors.lastname: VandeVondele
authors.forename: A Dieter
authors.initials: AD
authors.lastname: Schlüter