N-arylpyridinium molecules, 4,6-bis(4,4'-bipyridine-1-yl)-pyrimidine (1) and 3,6-bis(4,4'-bipyridine-1-yl)-pyridazine (2) and 3-pyridylviologen (3) were designed and synthesized as photoelectrochemically active ligands for coordination polymer assemblies with various ions. Their two-step reduction processes involving ion-radicals generation were observed in both electrochemical and photochemical processes. The photochemical ionradical formation in 1-3 were observed in the solid state. The magnetic behavior of Cu complex of 3 after light irradiation showed the antiferromagnetic interaction between photochemically generated ionradical and Cu spins.