Chiral lanthanide hexaazamacrocycles for circularly polarized luminescence, high relaxivity and magnetic resonance imaging

Tang, Yuxin; Jian, Minghong; Tang, Baobing; Zhu, Zhenhua; Wang, Zhenxin; Liu, Yunling

doi:10.1039/d4qi00275j

Inorg. Chem. Front.

2024

DOI: 10.1039/d4qi00275j

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Chiral lanthanide hexaazamacrocycles for circularly polarized luminescence, high relaxivity and magnetic resonance imaging

Yuxin Tang,

Minghong Jian,

Baobing Tang

et al.

Abstract: Multifunctional lanthanide complexes have been extensively studied in recent years owing to their widespread applications in physics, chemistry and biology, including quantum information processing, molecular spintronics and theranostics. The multifunctionality...

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Synthesis, crystal structures, characterization and luminescent thermal stability of Eu(III) and Gd(III) complex

Sun,

Xiang,

Huang

et al. 2024

Polyhedron

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Synthesis, crystal structures, characterization and luminescent thermal stability of Eu(III) and Gd(III) complex

Sun,

Xiang,

Huang

et al. 2024

Polyhedron

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Triple-Decker Hexaazamacrocyclic Lanthanide(III) Complexes: Structure, Magnetic Properties, and Temperature-Dependent Luminescence

Gawryszewska,

Ślepokura,

Lisowski

2024

Inorg. Chem.

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The reaction of fluoride anions with mononuclear rare-earth(III) complexes of the hexaazamacrocycle derived from 2,6-diformylpyridine and ethylenediamine affords trinuclear coordination compounds [Ln 3 L 3 (μ 2 -F) 4 (NO 3 ) 2 ](NO 3 ) 3 . The X-ray crystal structures of these complexes show triplex cationic complexes where the three roughly parallel macrocyclic lanthanide(III) units are linked by bis-μ2-F bridges. The detailed analysis of the photophysical properties of the [Eu 3 L 3 (μ 2 -F) 4 (NO 3 ) 2 ](NO 3 ) 3 ·2H 2 O and [Tb 3 L 3 (μ 2 -F) 4 (NO 3 ) 2 ](NO 3 ) 3 ·3H 2 O complexes reveals different temperature dependence of luminescence intensity and luminescence decay time of the Eu(III) and Tb(III) derivatives. The spectra of mixed species of average composition [Eu 1.5 Tb 1.5 L 3 (μ 2 -F) 4 (NO 3 ) 2 ](NO 3 ) 3 ·3H 2 O are in accordance with the ratiometric luminescent thermometer behavior. Measurements of the direct-current (dc) magnetic susceptibility of the [Dy 3 L 3 (μ 2 -F) 4 (NO 3 ) 2 ](NO 3 ) 3 ·2H 2 O complex indicate possible ferromagnetic interactions between the Dy(III) ions. Alternating current (ac) susceptibility measurements of this complex indicate single-molecule magnet behavior in zero dc field with magnetic relaxation dominated by Orbach mechanism and an effective energy barrier U eff = 12.3 cm–1 (17.7 K) with a pre-exponential relaxation time, τ0 of 7.3 × 10–6 s. A similar reaction of mononuclear macrocyclic complexes with a higher number of fluoride equivalents results in polymeric {[Ln 3 L 3 (μ 2 -F) 5 ](NO 3 ) 4 } n complexes. The X-ray crystal structure of the Nd(III) derivative of this type shows trinuclear units that are additionally linked by single fluoride bridges to form a linear coordination polymer.

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Chiral lanthanide hexaazamacrocycles for circularly polarized luminescence, high relaxivity and magnetic resonance imaging

Abstract: Multifunctional lanthanide complexes have been extensively studied in recent years owing to their widespread applications in physics, chemistry and biology, including quantum information processing, molecular spintronics and theranostics. The multifunctionality...

Cited by 2 publications

References 60 publications

Synthesis, crystal structures, characterization and luminescent thermal stability of Eu(III) and Gd(III) complex

Synthesis, crystal structures, characterization and luminescent thermal stability of Eu(III) and Gd(III) complex

Triple-Decker Hexaazamacrocyclic Lanthanide(III) Complexes: Structure, Magnetic Properties, and Temperature-Dependent Luminescence

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