TY - JOUR
T1 - Superatom Regiochemistry Dictates the Assembly and Surface Reactivity of a Two-Dimensional Material
AU - Bartholomew, Amymarie K.
AU - Meirzadeh, Elena
AU - Stone, Ilana B.
AU - Koay, Christie S.
AU - Nuckolls, Colin
AU - Steigerwald, Michael L.
AU - Crowther, Andrew C.
AU - Roy, Xavier
N1 - Publisher Copyright: © 2022 American Chemical Society
PY - 2022/1/26
Y1 - 2022/1/26
N2 - The area of two-dimensional (2D) materials research would benefit greatly from the development of synthetically tunable van der Waals (vdW) materials. While the bottom-up synthesis of 2D frameworks from nanoscale building blocks holds great promise in this quest, there are many remaining hurdles, including the design of building blocks that reliably produce 2D lattices and the growth of macroscopic crystals that can be exfoliated to produce 2D materials. Here we report the regioselective synthesis of the cluster [trans-Co6Se8(CN)4(CO)2]3–/4–, a “superatomic” building block designed to polymerize and assemble into a 2D cyanometalate lattice whose surfaces are chemically addressable. The resulting vdW material, [Co(py)4]2[trans-Co6Se8(CN)4(CO)2], grows as bulk single crystals that can be mechanically exfoliated to produce flakes as thin as bilayers, with photolabile CO ligands on the exfoliated surface. As a proof of concept, we show that these surface CO ligands can be replaced by 4-isocyanoazobenzene under blue light irradiation. This work demonstrates that the bottom-up assembly of layered vdW materials from superatoms is a promising and versatile approach to create 2D materials with tunable physical and chemical properties.
AB - The area of two-dimensional (2D) materials research would benefit greatly from the development of synthetically tunable van der Waals (vdW) materials. While the bottom-up synthesis of 2D frameworks from nanoscale building blocks holds great promise in this quest, there are many remaining hurdles, including the design of building blocks that reliably produce 2D lattices and the growth of macroscopic crystals that can be exfoliated to produce 2D materials. Here we report the regioselective synthesis of the cluster [trans-Co6Se8(CN)4(CO)2]3–/4–, a “superatomic” building block designed to polymerize and assemble into a 2D cyanometalate lattice whose surfaces are chemically addressable. The resulting vdW material, [Co(py)4]2[trans-Co6Se8(CN)4(CO)2], grows as bulk single crystals that can be mechanically exfoliated to produce flakes as thin as bilayers, with photolabile CO ligands on the exfoliated surface. As a proof of concept, we show that these surface CO ligands can be replaced by 4-isocyanoazobenzene under blue light irradiation. This work demonstrates that the bottom-up assembly of layered vdW materials from superatoms is a promising and versatile approach to create 2D materials with tunable physical and chemical properties.
UR - http://www.scopus.com/inward/record.url?scp=85123873160&partnerID=8YFLogxK
U2 - https://doi.org/10.1021/jacs.1c12072
DO - https://doi.org/10.1021/jacs.1c12072
M3 - مقالة
C2 - 35020382
SN - 0002-7863
VL - 144
SP - 1119
EP - 1124
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 3
ER -