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). Key design innovations leverage large-sized porphyrins to suppress intrachain antiferromagnetic coupling, while ${Zn}^{2+}$ chelation at porphyrin cores enhances molecule-substrate interactions to amplify Kondo effect. High-resolution STS measurements and low-energy effective modeling collectively demonstrate that ${\pi}$-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, geometric control emerges through conformational distortions modulated by chain fusion width. This enables directional tuning of the competition between Kondo screening and magnetic exchange. Tilted single/fused-triple-porphyrin chains weaken spin exchange through enhanced Kondo coupling, while parallel fused-double-porphyrin chains suppress Kondo screening via increased spin exchange. This opposing modulation of Kondo versus exchange interactions establishes an inverse control paradigm. 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.