Step-by-Step Electrocrystallization Processes to Make Multiblock Magnetic Molecular Heterostructures

Abstract

Assembling conductive or magnetic heterostructures by bulk inorganic materials is important for making functional electronic or spintronic devices, such as semiconductive p-doped and n-doped silicon for P–N junction diodes, alternating ferromagnetic and nonmagnetic conductive layers used in giant magnetoresistance (GMR). Nonetheless, there have been few demonstrations of conductive or magnetic heterostructures made by discrete molecules. It is of fundamental interest to prepare and investigate heterostructures based on molecular conductors or molecular magnets, such as single-molecule magnets (SMMs). Herein, we demonstrate the fabrication of a series of molecular heterostructures composed of (TTF)2M(pdms)2 (TTF = tetrathiafulvalene, M = Co(II), Zn(II), Ni(II), H2pdms = 1,2-bis(methanesulfonamido)benzene) multiple building blocks through a well-controlled step-by-step electrocrystallization growth process, where the Co(pdms)2, Ni(pdms)2, and Zn(pdms)2 anionic complex is a SMM, paramagnetic, and diamagnetic molecule, respectively. Magnetic and SMM properties of the heterostructures were characterized and compared to the parentage (TTF)2Co(pdms)2 complex. This study presents the first methodology for creating molecule-based magnetic heterostructural systems by electrocrystallization.

Double core-shell semiconducting molecular-chain halogen- bridged metal complexes with ohmic contact heterojunctions

“…It is the first example of a molecule-based heterostructure that has electronic conductivity, since other reported molecule-based heterostructures are less conductive or do not conduct at all due to poor connections at the heterojunction. [40][41][42] Doping the MX-Chains has been tried previously, 28,36,[43][44][45] although it only afforded minor changes of the electrical conductivity and it has not been possible to obtain MX-Chains which clearly exhibit p-type semiconduction. The synthesis of p-type MX-Chains, the creation of a p-n heterojunction, and the challenge of fabricating a 1D electronic system will be considered in future works.…”