A lateral heterojunction, fabricated by spatially confined transmetallation of a precursor zinc(II) benzenehexathiolato coordination nanosheet with Fe(II) and Cu(II) ions is reported. Structural differences between the transmetallated and the as-prepared nanosheets lead to physical and chemical differences. Band structure bending across the interface of the transmetallated nanosheets results in the observed rectifying behavior. Abstract Heterostructures of two-dimensional materials realise novel and enhanced physical phenomena, making them attractive research targets. Compared to inorganic materials, coordination nanosheets have virtually infinite combinations, leading to tunability of physical properties and are promising candidates for heterostructure fabrication. Although stacking of coordination materials into vertical heterostructures is widely reported, reports of lateral coordination material heterostructures are few. Here we show the successful fabrication of a seamless lateral heterojunction showing diode behaviour, by sequential and spatially limited immersion of a new metalladithiolene coordination nanosheet, Zn3BHT, into aqueous Cu(II) and Fe(II) solutions. Upon immersion, the Zn centres in insulating Zn3BHT are replaced by Cu or Fe ions, resulting in conductivity. The transmetallation is spatially confined, occurring only within the immersed area. We anticipate that our results will be a starting point towards exploring transmetallation of various two-dimensional materials to produce lateral heterojunctions, by providing a new and facile synthetic route.
Published in: "Angewandte Chemie International Edition".