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