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 non-monotonically 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.