Superatom Regiochemistry Dictates the Assembly and Surface Reactivity of a Two-Dimensional Material
Superatom Regiochemistry Dictates the Assembly and Surface Reactivity of a Two-Dimensional Material
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DOI：
10.1021/jacs.1c12072
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发表时间：
2022-01-12
影响因子：
15
通讯作者：
Roy, Xavier
中科院分区：
文献类型：
--
作者：
Bartholomew, Amymarie K.;Meirzadeh, Elena;Roy, Xavier
合成可调谐范德华(VDW)材料的发展将使二维材料研究领域受益匪浅。虽然从纳米级构建块自下而上地合成2D框架在这一探索中前景光明，但仍有许多障碍，包括可靠地产生2D晶格的构建块的设计，以及可以剥离以生产2D材料的宏观晶体的生长。在这里，我们报道了区域选择性地合成了簇合物[trans-Co6Se8(CN)(4)(CO)(2)](3-/4-)，这是一种旨在聚合和组装成2D氰基金属酸盐晶格的超原子构筑块，其表面是化学可寻址的。由此得到的VDW材料[Co(Py)(4)](2)[trans-Co6Se8(CN)(4)-(CO)(2)]以大块单晶的形式生长，可以被机械剥离以产生与双层一样薄的片状，剥离的表面上具有耐光性的CO配体。作为概念的证明，我们证明了在蓝光照射下，这些表面的CO配体可以被4-异氰基偶氮苯取代。这项工作表明，由超原子自下而上组装层状VDW材料是一种很有前途的、通用的方法，可以制造出具有可调物理化学性质的2D材料。
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.