Octopus ‐Type Crown‐Bisphthalocyaninate Anchor for Bottom‐Up Assembly of Supramolecular Bilayers with Expanded Redox‐Switching Capability

A new heteroleptic bisphthalocyaninate with one ligand bearing eight thioacetate terminated “tentacles” and one tetra-crown substituted ligand is synthesized. Self-assembled monolayer based on this complex is formed on gold. Supramolecular crown-ether–potassium interaction is then used to append tetra-crown-phthalocyanine adlayer that provides another available redox-state in the nan oscale system, totaling four, which can all be read-out optically. AbstractAchievement of information storage at molecular level remains a pressing task in miniaturization of computing technology. One of the promising approaches for its practical realization is development of nanoscale molecular switching materials including redox-active systems. The present work demonstrates a concept of expansion of a number of available redox-states of self-assembled monolayers through supramolecular approach. For this, the authors synthesized an octopus-like heteroleptic terbium(III) bisphthalocyaninate bearing one ligand with eight thioacetate-terminated “tentacles” (octopus-Pc) and a ligand with four crown-ether moieties (H2[(15C5)4Pc]). It is shown thatoctopus-Pc forms stable monolayers on gold, where its face-on orientation allows for subsequent binding of crown-phthalocyanine molecules via potassium ion bridges. This chemistry is utilized to form a heterogeneous bilayer, in which a single molecule thick adlayer brings an additional redox-state to the system, thus expanding the multistability of...
Source: Small - Category: Nanotechnology Authors: Tags: Research Article Source Type: research