The association of lanthanide ions and paracyclophane derivatives has been very scarcely reported in the literature. In this study, elaboration of five coordination lanthanide complexes involving the 1,4(1,4)-dibenzenacyclohexaphane-1²,4³-diylbis(diphenylphosphine oxide) ligand (L) was achieved with the determination of single-crystal X-ray diffraction structures of four mononuclear complexes of formula [Ln(hfac)₃(L)] (hfac- = 1,1,1,5,5,5-hexafluoroacetylacetonate) (Ln = Dy(III) (1-Dy) and Yb(III) (2-Yb)) and [Ln(tta)₃(L)] (tta⁻ = 2-tenoyl-trifluoroacetylacetonate) (Ln = Dy(III) (3-Dy) and Yb(III) (4-Yb)) and one dinuclear complex [Na(Dy₂(hfac)₆(L)₂)](BArF) (BArF⁻ = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) (5-Dy). The compounds were characterized using elemental analysis, IR spectroscopy, DC and AC magnetic measurements and photophysical investigations. L is an efficient organic chromophore for the sensitization of both visible Dy(III) (1-Dy) and near-infrared Yb(III) (2-Yb and 4-Yb) luminescence. The combination of excitation and emission spectra allowed the determination of the crystal field spitting of both the ²F_7/2 ground state and ²F_5/2 excited state for 2-Yb and 4-Yb. Moreover, 3-Dy and the two Yb(III) derivatives displayed field-induced single-molecule magnet (SMM) behaviour with slow magnetic relaxation occurring through the Raman process only for 2-Yb and 4-Yb, whereas a combination of Orbach and Raman processes was identified for 3-Dy.

中文翻译：

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稀土发光[2.2]对环芳基单分子磁体中的磁结构相关性

文献中很少报道镧系离子和对环芳烷衍生物的缔合。本研究通过单晶X射线测定，详细阐述了涉及1,4(1,4)-二苯并环六烷-1 ² ,4 ^{3 -}二基双(二苯基氧化膦)配体( L )的五种配位稀土配合物。式 [Ln(hfac) ₃ ( L )] (hfac- = 1,1,1,5,5,5-六氟乙酰丙酮) (Ln = Dy( III ) ( 1-Dy ) 和 Yb的四种单核络合物的衍射结构( III ) ( 2-Yb )) 和 [Ln(tta) ₃ ( L )] (tta ⁻ = 2-烯酰基三氟乙酰丙酮) (Ln = Dy( III ) ( 3-Dy ) 和 Yb( III ) ( 4- Yb )) 和一种双核配合物 [Na(Dy ₂ (hfac) ₆ ( L ) ₂ )](BArF) (BArF ⁻ = 四[3,5-双(三氟甲基)苯基]硼酸盐) ( 5-Dy )。使用元素分析、红外光谱、直流和交流磁测量以及光物理研究对这些化合物进行了表征。 L 是一种高效的有机发色团，可敏化可见 Dy( III ) ( 1-Dy ) 和近红外 Yb( III )（2-Yb和4-Yb）发光。激发和发射光谱的组合允许确定2-Yb和4-Yb的² F _7/2基态和² F _5/2激发态的晶体场分裂。此外，3-Dy和两种 Yb( III ) 衍生物表现出场致单分子磁体 (SMM) 行为，仅2-Yb和4-Yb通过拉曼过程发生缓慢磁弛豫，而 Orbach 和确定了3-Dy的拉曼过程。