N-arylpyridinium molecules, 4, 6-bis(4,4′-bipyridine-1-y1)-pyrimidine (1) and 3,6-bis(4,4′-bipyridine-1-y1)-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 in1–3were observed in the solid state. The magnetic behavior of Cu complex of3after light irradiation showed the antiferromagnetic interaction between photochemically generated ionradical and Cu spins.