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Switching of Single‐Molecule Magnetic Properties of Tb III –Porphyrin Double‐Decker Complexes and Observation of Their Supramolecular Structures on a Carbon Surface
Author(s) -
Inose Tomoko,
Tanaka Daisuke,
Tanaka Hirofumi,
Ivasenko Oleksandr,
Nagata Toshi,
Ohta Yusuke,
De Feyter Steven,
Ishikawa Naoto,
Ogawa Takuji
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402669
Subject(s) - porphyrin , supramolecular chemistry , protonation , chemistry , molecule , crystallography , spintronics , scanning tunneling microscope , double bond , ligand (biochemistry) , cyclophane , stereochemistry , photochemistry , nanotechnology , materials science , crystal structure , ferromagnetism , polymer chemistry , physics , organic chemistry , ion , receptor , quantum mechanics , biochemistry
Double‐decker complexes based on single‐molecule magnets (SMMs) are a class of highly promising molecules for applications in molecular spintronics, wherein control of both the ligand oxidative states and the 2D supramolecular structure on carbon materials is of great importance. This study focuses on the synthesis and study of 2,3,7,8,12,13,17,18‐octaethylporphyrin (OEP)–Tb III double‐decker complexes with different electronic structures comprising protonated, anionic, and radical forms. Magnetic susceptibility measurements revealed that only the anionic and radical forms of the OEP–Tb III double‐decker complexes exhibited SMM properties. The barrier heights for magnetic moment reversal were estimated to be 207 and 215 cm −1 for the anionic and radical forms, respectively. Scanning tunneling microscopy (STM) investigations revealed that these OEP–Tb III complexes form well‐ordered monolayers upon simple dropcasting from dilute dichloromethane solutions. All three complexes form an isomorphic pseudo‐hexagonal 2D pattern, regardless of the differences in the electronic structures of their porphyrin–Tb cores. This finding is of interest for SMM technology as ultrathin films of these materials undergoing chemical transformations will not require any detrimental reorganization. Finally, we demonstrate self‐assembly of the protonated 5,15‐bisdodecylporphyrin (BDP)–Tb III double‐decker complex as an example of successful supramolecular design to achieve controlled alignment of SMM‐active sites.