Construction of Kondo Chains by Engineering Porphyrin π-Radicals on Au(111)

Abstract

Quantum manipulation of molecular radical spins provides a crucial platform for exploring emergent phenomena in many-body systems. Here, we combine surface-confined synthesis with scanning tunneling microscopy (STM) tip-induced dehydrogenation to achieve atom-precise engineering of quasi-one-dimensional porphyrin-based Kondo chains (1–7 units) on Au(111). High-resolution STS measurements and low-energy effective modeling collectively demonstrate that π-radicals at each fused-porphyrin unit form Kondo singlets screened by conduction electrons. Adjacent singlets develop direct coherent coupling via quantum-state-overlap-enabled electron tunneling. Crucially, chiral symmetry in the effective model governs zero-mode distribution─present in odd-length chains yet absent in even-length chains─which dictates pronounced odd–even quantum effects in STS spectra of finite chains. Furthermore, the number of parallel porphyrin chains nonmonotonically tunes the competition between the Kondo effect and spin exchange, showing opposing trends in strength and demonstrating that both wave function overlap and the SOMO–LUMO gap collectively govern these interactions. This work simultaneously resolves the dimensional dependence of many-body correlations in confined quantum systems and pioneers approaches for quantum-critical manipulation in molecular spin architectures.