We describe a new approach to synthesize two-dimensional (2D) nanosheets from the bottom-up. We functionalize redox-active superatoms with groups that can direct their assembly into multidimensional solids. We synthesized Co₆Se₈[PEt₂(4-C₆H₄COOH)]₆ and found that it forms a crystalline assembly. The solid-state structure is a three-dimensional (3D) network in which the carboxylic acids form intercluster hydrogen bonds. We modify the self-assembly by replacing the reversible hydrogen bonds that hold the superatoms together with zinc carboxylate bonds via the solvothermal reaction of Co₆Se₈[PEt₂(4-C₆H₄COOH)]₆ with Zn(NO₃)₂. We obtain two types of crystalline materials using this approach: one is a 3D solid and the other consists of stacked layers of 2D sheets. The dimensionality is controlled by subtle changes in reaction conditions. These 2D sheets can be chemically exfoliated, and the exfoliated, ultrathin 2D layers are soluble. After they are deposited on a substrate, they can be imaged. We cast them onto an electrode surface and show that they retain the redox activity of the superatom building blocks due to the porosity in the sheets.

中文翻译：

---

氧化还原活性超原子的二维纳米片

我们描述了一种自下而上地合成二维（2D）纳米片的新方法。我们通过可引导其组装成多维固体的基团对氧化还原活性超原子进行功能化。我们合成了Co ₆ Se ₈ [PEt ₂（4-C ₆ H ₄ COOH）] ₆，发现它形成了晶体组件。固态结构是三维（3D）网络，其中的羧酸形成簇间氢键。我们通过Co ₆ Se ₈ [PEt ₂（4-C₆ H ₄ COOH）] ₆与Zn（NO ₃）₂。我们使用这种方法获得两种类型的晶体材料：一种是3D实体，另一种是由2D图纸的堆叠层组成。通过反应条件的细微变化来控制尺寸。这些2D薄片可以被化学剥落，并且剥落的超薄2D层是可溶的。在将它们沉积在基板上之后，可以对其进行成像。我们将它们浇铸在电极表面上，并显示出由于薄板中的孔隙率，它们保留了超原子构件的氧化还原活性。