TY - JOUR
T1 - Ligand Rotation Induced Oxidation State Change and Spin Appearance of the Bis(phthalocyaninato)cerium (CePc2) Molecule on the Au(111) Surface
AU - Saiful, Islam
AU - Hossain, Mohammad Ikram
AU - Katoh, Keiichi
AU - Yamashita, Masahiro
AU - Arafune, Ryuichi
AU - Shahed, Syed Mohammad Fakruddin
AU - Komeda, Tadahiro
N1 - Funding Information:
This study was supported in part by Grant-in-Aid for Scientific Research (S) (no. 19H05621) (Tadahiro Komeda) (Tadahiro Komeda) and by the National Natural Science Foundation of China (NSFC 21971124 and 22150710513). M.Y. thanks the support from the 111 projects (B18030) from China. The DFT calculations were performed using National Institute for Materials Science (Numerical Material Simulator Station) computer facilities. RA gratefully acknowledges significant financial support from the World Premier International Research Center Initiative (WPI) on Materials Nanoarchitectonics (MANA).
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/10/13
Y1 - 2022/10/13
N2 - We demonstrate that a nonmagnetic molecule is changed into magnetic when its internal structure is rotated by forming an ordered film on a metal surface. We used a double-decker complex, bis(phthalocyaninato)cerium (CePc2), where the valence of the Ce atom changes between +3 and +4 with a small energy barrier. CePc2is nonmagnetic in bulk and becomes magnetic in the monolayer film on Au(111). The intra-molecular structure and the magnetic property are revealed using scanning tunneling microscopy/spectroscopy. We attribute the mechanism to a change of the rotational angle (θ) between the upper and lower Pc ligands, driven by the steric repulsive force originating from forming an almost square lattice on Au(111). The θ changes from θ = 45° of the bulk value into θ = 0° for the film. GGA + U calculation indicates that the change from θ = 45° to θ = 0° causes the Ce valence change from the nonmagnetic +4 state into the magnetic +3 state.
AB - We demonstrate that a nonmagnetic molecule is changed into magnetic when its internal structure is rotated by forming an ordered film on a metal surface. We used a double-decker complex, bis(phthalocyaninato)cerium (CePc2), where the valence of the Ce atom changes between +3 and +4 with a small energy barrier. CePc2is nonmagnetic in bulk and becomes magnetic in the monolayer film on Au(111). The intra-molecular structure and the magnetic property are revealed using scanning tunneling microscopy/spectroscopy. We attribute the mechanism to a change of the rotational angle (θ) between the upper and lower Pc ligands, driven by the steric repulsive force originating from forming an almost square lattice on Au(111). The θ changes from θ = 45° of the bulk value into θ = 0° for the film. GGA + U calculation indicates that the change from θ = 45° to θ = 0° causes the Ce valence change from the nonmagnetic +4 state into the magnetic +3 state.
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U2 - 10.1021/acs.jpcc.2c04234
DO - 10.1021/acs.jpcc.2c04234
M3 - Article
AN - SCOPUS:85139416005
SN - 1932-7447
VL - 126
SP - 17152
EP - 17163
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 40
ER -