Data for paper: Triply Bonded Pancake π-Dimers Stabilized by Tetravalent Actinides

Data for paper published Feb 05 2024 in <i>the Journal of the American Chemical Society (JACS)</i>IR spectroscopy data.Crystallography data in CIF format.NMR spectroscopy data.EPR spectroscopy data.UV/vis/NIR spectroscopy data.Conductivity data.Thin film characterization data.DFT optimized geometries for 1-Th and 1-U.AbstractAromatic 𝝅-stacking is a weakly attractive, non-covalent interaction often found in biological macromolecules and syn-thetic supramolecular chemistry. The weak non-directional nature of 𝝅-stacking can present challenges in the design of materials owing to their weak, non-directional nature. However, when aromatic 𝝅-systems contain an unpaired electron, stronger attraction involving face-to-face 𝝅-orbital overlap is possible, resulting in covalent so-called ‘pancake’ bonds. Two-electron, multicentre single pancake bonds are well-known whereas four-electron double pancake bonds are rare. Higher-order pancake bonds have been predicted, but experimental systems are unknown. Here, we show that six-electron triple pancake bonds can be synthesized by threefold reduction of hexaazatrinaphthylene (HAN) and subse-quent stacking of the [HAN]³– tri-radicals. Our analysis reveals a multicentre covalent triple pancake bond consisting of a 𝝅-orbital and two equivalent 𝝅-orbitals. An electrostatic stabilizing role is established for tetravalent thorium and urani-um ions in these systems. We also show that the electronic absorption spectrum of the triple pancake bonds closely matches computational predictions, providing experimental verification of these unique interactions. The discovery of conductivity in thin films of the triply bonded 𝝅-dimers presents new opportunities for the discovery of single-component molecular conductors and other spin-based molecular materials<br>