Actinide Coordination Chemistry on Surfaces: Synthesis, Manipulation, and Properties of Thorium Bis(porphyrinato) Complexes

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.