Actinide-based metal–organic complexes and coordination architectures encompass intriguing properties and functionalities but are still largely unexplored on surfaces. We introduce the in situ synthesis of actinide tetrapyrrole complexes under ultrahigh-vacuum conditions, on both a metallic support and a 2D material. Specifically, exposure of a tetraphenylporphyrin (TPP) multilayer to an elemental beam of thorium followed by a temperature-programmed reaction and desorption of surplus molecules yields bis(porphyrinato)thorium (Th(TPP)₂) assemblies on Ag(111) and hexagonal boron nitride/Cu(111). A multimethod characterization including X-ray photoelectron spectroscopy, scanning tunneling microscopy, temperature-programmed desorption, and complementary density functional theory modeling provides insights into conformational and electronic properties. Supramolecular assemblies of Th(TPP)₂ as well as individual double-deckers are addressed with submolecular precision, e.g., demonstrating the reversible rotation of the top porphyrin in Th(TPP)₂ by molecular manipulation. Our findings thus demonstrate prospects for actinide-based functional nanoarchitectures.

中文翻译：

---

表面锕系配位化学：钍双（卟啉）配合物的合成、操作和性质

基于锕系元素的金属-有机配合物和配位结构包含有趣的特性和功能，但在表面上仍然很大程度上未被探索。我们介绍了在超高真空条件下，在金属载体和二维材料上原位合成锕系四吡咯配合物。具体来说，将四苯基卟啉 (TPP) 多层暴露于钍元素束，然后进行程序升温反应和多余分子的解吸产生双（卟啉）钍 (Th(TPP) ₂) 在 Ag(111) 和六方氮化硼/Cu(111) 上组装。包括 X 射线光电子能谱、扫描隧道显微镜、程序升温解吸和互补密度泛函理论建模在内的多方法表征提供了对构象和电子特性的见解。Th(TPP) _{2 的}超分子组装以及单个双层以亚分子精度解决，例如，通过分子操作证明Th(TPP) _{2 中}顶部卟啉的可逆旋转。因此，我们的发现证明了基于锕系元素的功能纳米结构的前景。