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

Assemblingconductive or magnetic heterostructures by bulk inorganicmaterials is important for making functional electronic or spintronicdevices, such as semiconductive p-doped and n-doped silicon for P-Njunction diodes, alternating ferromagnetic and nonmagnetic conductivelayers used in giant magnetoresistance (GMR). Nonetheless, there havebeen few demonstrations of conductive or magnetic heterostructuresmade by discrete molecules. It is of fundamental interest to prepareand investigate heterostructures based on molecular conductors ormolecular magnets, such as single-molecule magnets (SMMs). Herein,we demonstrate the fabrication of a series of molecular heterostructurescomposed of (TTF)(2)M(pdms)(2) (TTF = tetrathiafulvalene,M = Co(II), Zn(II), Ni(II), H(2)pdms = 1,2-bis(methanesulfonamido)benzene)multiple building blocks through a well-controlled step-by-step electrocrystallizationgrowth 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 propertiesof the heterostructures were characterized and compared to the parentage(TTF)(2)Co(pdms)(2) complex. This study presentsthe first methodology for creating molecule-based magnetic heterostructuralsystems by electrocrystallization.

Automated summary

Constructing heterostructures based on molecular conductors or molecular magnets is important, and this study demonstrates the fabrication of molecular heterostructures composed of (TTF)(2)M(pdms)(2) through a controlled electrocrystallization process. The magnetic and single-molecule magnet properties of the heterostructures were characterized and compared to the parent (TTF)(2)Co(pdms)(2) complex, providing a new methodology for creating molecule-based magnetic heterostructures.