TY - JOUR
T1 - Manipulation of the Coordination Geometry along the C4 Rotation Axis in a Dinuclear Tb3+ Triple-Decker Complex via a Supramolecular Approach
AU - Katoh, Keiichi
AU - Yasuda, Nobuhiro
AU - Damjanović, Marko
AU - Wernsdorfer, Wolfgang
AU - Breedlove, Brian K.
AU - Yamashita, Masahiro
N1 - Funding Information:
This work was partially supported by a Grant‐in‐Aid for Scientific Research (C) (grant no. 15K05467), Grant‐in‐Aid for Young Scientists (B) (grant no. 24750119), Grant‐in‐Aid for Scientific Research (S) (grant no. 20225003) from the Ministry of Education, Culture, Sports, Science, Technology, Japan (MEXT), CREST (JPMJCR12L3) from JST. M.Y. thanks the support from the 111 Project (B18030) from China. W.W. thanks the support from the ERC Grant MoQuOS 741276.
Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/4/9
Y1 - 2020/4/9
N2 - A supramolecular complex (1⋅C60) was prepared by assembling (C60-Ih)[5,6]fullerene (C60) with the dinuclear Tb3+ triple-decker complex [(TPP)Tb(Pc)Tb(TPP)] (1: Tb3+=trivalent terbium ion, Pc2−=phthalocyaninato, TPP2−=tetraphenylporphyrinato) with quasi-D4h symmetry to investigate the relationship between the coordination symmetry and single-molecule magnet (SMM) properties. Tb3+-Pc triple-decker complexes (Tb2Pc3) have an important advantage over Tb3+-Pc double-decker complexes (TbPc2) since the magnetic relaxation processes correspond to the Zeeman splitting when there are two 4f spin systems. The two Tb3+ sites of 1 are equivalent, and the twist angle (φ) was determined to be 3.62°. On the other hand, the two Tb3+ sites of 1⋅C60 are not equivalent. The φ values for sites Tb1 and Tb2 were determined to be 3.67° and 33.8°, respectively, due to a change in the coordination symmetry of 1 upon association with C60. At 1.8 K, 1 and 1⋅C60 undergo different magnetic relaxations, and the changes in the ground state affect the spin dynamics. Although 1 and 1⋅C60 relax via QTM in a zero applied magnetic field (H), H dependencies of the magnetic relaxation times (τ) for H>1500 Oe are similar. On the other hand, for H<1500 Oe, the τ values have different behaviors since the off-diagonal terms ((Formula presented.)) affect the magnetic relaxation mechanism. From temperature (T) and H dependences of τ, spin-phonon interactions along with direct and Raman mechanisms explain the spin dynamics. We believe that a supramolecular method can be used to control the magnetic anisotropy along the C4 rotation axis and the spin dynamic properties in dinuclear Ln3+-Pc multiple-decker complexes.
AB - A supramolecular complex (1⋅C60) was prepared by assembling (C60-Ih)[5,6]fullerene (C60) with the dinuclear Tb3+ triple-decker complex [(TPP)Tb(Pc)Tb(TPP)] (1: Tb3+=trivalent terbium ion, Pc2−=phthalocyaninato, TPP2−=tetraphenylporphyrinato) with quasi-D4h symmetry to investigate the relationship between the coordination symmetry and single-molecule magnet (SMM) properties. Tb3+-Pc triple-decker complexes (Tb2Pc3) have an important advantage over Tb3+-Pc double-decker complexes (TbPc2) since the magnetic relaxation processes correspond to the Zeeman splitting when there are two 4f spin systems. The two Tb3+ sites of 1 are equivalent, and the twist angle (φ) was determined to be 3.62°. On the other hand, the two Tb3+ sites of 1⋅C60 are not equivalent. The φ values for sites Tb1 and Tb2 were determined to be 3.67° and 33.8°, respectively, due to a change in the coordination symmetry of 1 upon association with C60. At 1.8 K, 1 and 1⋅C60 undergo different magnetic relaxations, and the changes in the ground state affect the spin dynamics. Although 1 and 1⋅C60 relax via QTM in a zero applied magnetic field (H), H dependencies of the magnetic relaxation times (τ) for H>1500 Oe are similar. On the other hand, for H<1500 Oe, the τ values have different behaviors since the off-diagonal terms ((Formula presented.)) affect the magnetic relaxation mechanism. From temperature (T) and H dependences of τ, spin-phonon interactions along with direct and Raman mechanisms explain the spin dynamics. We believe that a supramolecular method can be used to control the magnetic anisotropy along the C4 rotation axis and the spin dynamic properties in dinuclear Ln3+-Pc multiple-decker complexes.
KW - coordination modes
KW - fullerenes
KW - magnetic properties
KW - single-molecule magnets
KW - spin dynamics
KW - supramolecular chemistry
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U2 - 10.1002/chem.201905400
DO - 10.1002/chem.201905400
M3 - Article
C2 - 31984579
AN - SCOPUS:85082198533
VL - 26
SP - 4805
EP - 4815
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 21
ER -