Relationship between Torsion and Anisotropic Exchange Coupling in a TbIII-Radical-Based Single-Molecule Magnet

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• 作者：Michael L. Baker ; Takuya Tanaka ; Rina Murakami ; Seiko Ohira-Kawamura ; Kenji Nakajima ; Takayuki Ishida ; Hiroyuki Nojiri
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：June 15, 2015
• 年：2015
• 卷：54
• 期：12
• 页码：5732-5738
• 全文大小：461K
• ISSN：1520-510X

文摘

The incorporation of paramagnetic ligands within rare-earth ion clusters exhibiting large magnetic anisotropy has provided significant advancement in the design of single-molecule magnets (SMMs) with large blocking temperatures. However, the exchange interaction in such systems is complex and difficult to probe by conventional magnetometry techniques, and little is known about the structural relationships. Inelastic neutron scattering and terahertz electron paramagnetic resonance measurements are used complimentarily to investigate the large exchange interaction between a rare earth鈥搑adical pair in a Tb^III-based SMM complex. The origin of the exchange interaction is investigated for two molecular species in the crystallographic unit cell that exhibit different bonding structures between Tb^III and a 2pyNO radical. A correlation between the Tb鈥揙鈥揘鈥揅 torsion angles and the magnitudes of exchange couplings is found. Interestingly, a large nondegeneracy within the ground-state doublet is present for the larger torsion angle species. It is essential to consider the balance of two channels of exchange coupling, 2p鈥?f hybridization and 2p鈥?d charge transfer, to explain this characteristic behavior. The former channel gives the antiferromagnetic interaction, and the latter gives the ferromagnetic one. When an effective 拇 = ¹/₂ Ising-type Hamiltonian is applied, the exchange couplings are evaluated to be antiferromagnetic J^z = 9.89 meV (79.8 cm^鈥?) for the low torsion angle (3.8掳) species and J^z = 7.39 meV (59.6 cm^鈥?) for the larger torsion angle (15.8掳) species. It is also found that a small percentage of the transverse exchange component must be included for the larger torsion angle to account for the observed nondegenerate ground state. The symmetry of the exchange couplings is discussed by considering the characters of d and f orbitals.