Polycyclic aromatic hydrocarbon serves as an Ag⁺ sponge for in situ transformation from diamagnetic coordination...

Coordination polymers (CPs) are crucial for the design of tunable architectures and functional materials. Nevertheless, the application of polycyclic aromatic hydrocarbons (PAHs) as ligands has been largely restricted to nitrogen-doped PAHs, whereas non-nitrogen heteroatom-doped PAHs remain scarcely explored. In this work, we employ a selenium-containing PAH (4Se-PAH) to construct novel radical cations and CPs. By adjusting the molar ratio of 4Se-PAH to AgNTf₂, the reaction outcome can be precisely controlled. A 1 : 1 ratio preferentially promotes oxidation, affording a stable monomeric radical cation salt (R1). In contrast, higher AgNTf₂ ratios (1 : 2 or 1 : 3) induce simultaneous oxidation and coordination, producing R1 along with two one-dimensional silver CPs (M1 and M2). Remarkably, these CPs undergo chemical transformation in CH₂Cl₂, generating the radical cation and metallic silver, representing a rare dissociation-oxidation conversion from diamagnetic CPs to paramagnetic radical species. Furthermore, M2 exhibits pronounced selectivity toward CH₂Cl₂ and 1,2-dichloroethane, producing a deep green color in these solvents. This study presents a novel strategy that integrates oxidation and coordination chemistry within a single system and demonstrates the potential of heteroatom-doped PAHs as versatile building blocks for stimuli-responsive multifunctional materials.