Platinum(II)-Based Metallo-Supramolecular Polymer with Controlled Unidirectional Dipoles for Tunable Rectification.

A platinum(II)-based, luminescent, metallo-supramolecular polymer (PolyPtL1) having an inherent dipole moment was synthesized via complexation of Pt(II) ions with an asymmetric ligand L1, containing terpyridyl and pyridyl moieties. The synthesized ligand and polymer were well characterized by various NMR techniques, optical spectroscopy, and cyclic voltammetry studies. The morphological study by atomic force microscopy revealed the individual and assembled polymer chains of 1-4 nm height. The polymer was specifically attached on Au-electrodes to produce two types of film (films 1 and 2) in which the polymer chains were aligned with their dipoles in opposite directions. The Au-surface bounded films were characterized by UV-vis, Raman spectroscopy, cyclic voltammetry, and atomic force microscopy study. The quantum mechanical calculation determined the average dipole moment for each monomer unit in PolyPtL1 to be about 5.8 D. The precise surface derivatization permitted effective tuning of the direction dipole moment, as well as the direction of rectification of the resulting polymer-attached molecular diodes. Film 1 was more conductive in positive bias region with an average rectification ratio (RR = I(+4 V)/I(-4 V)) ≈ 20, whereas film 2 was more conducting in negative bias with an average rectification ratio (RR = I(-4 V)/I(+4 V)) ≈ 18.