To understand how metal-ligand coordination promotes the ionic conductivity of a polymer, we choose low molecular weight PDMS as the polymer precursor because of its many advantageous features. First, PDMS has a low glass transition temperature (T g ≈ -123 ℃), yielding dynamic chain motion at room temperature, which facilitates the transport of ions. Second, PDMS has low inherent ion impurity content and low dielectric constant (κ ≈ 2.3-2.8), which serves as a non-conductive baseline and creates a clear contrast in the ionic conductivity of the polymer before and after introducing metal-ligand coordination. Furthermore, ion interaction in the system is mainly mediated by the metal-ligand coordination rather than the solvation of polymer backbone, which offers us a good model to decouple the effect of metal-ligand coordination from other factors that contribute to the ionic conductivity. Third, PDMS has many good physical and chemical properties such as being stretchable and inert. Finally, PDMS is easy to fabricate and low cost, which makes it a popular material candidate for next-generation ionic devices. We create a model system by functionalizing the ends of low molecular weight PDMS with a metal coordinating ligand. Pyridyl imine is selected as the functional group because it is a versatile ligand that can coordinate with various metal cations. The model system (PDMS-L, L represents ligand functionalization) is synthesized via a condensation reaction between aminopropyl terminated PDMS and 2-pyridinecarboxaldehyde according to a previously reported procedure, yielding a yellow oil-like product (Figure ). The structure of PDMS-L is confirmed by 1 H NMR (Figure ). Based on the ratio of the hydrogen atoms in the dimethylsiloxane backbone to the hydrogen atoms in the pyridyl imine end groups, which is calculated from the integration of different peak area in the 1 H NMR spectrum, the number average molecular weight (M n ) of PDMS-L is around 2000 g/mol.