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Four new rare-earth nitronyl nitroxide radical complexes: Magnetic and luminescent properties.

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Title: Four new rare-earth nitronyl nitroxide radical complexes: Magnetic and luminescent properties.
Authors: Yang, Shuai-Liang1, Wang, Rui-Rui1, Jin, Xiao-Jiao1, Zhang, Chen-Xi1,2 zcx@tust.edu.cn, Wang, Qing-Lun3,4
Source: Polyhedron. Apr2018, Vol. 144, p101-106. 6p.
Subjects: Luminescence, Crystal structure, Fluorine compounds, Analytical chemistry, Heat resistant alloys
Abstract: Four new rare-earth nitronyl nitroxide radical complexes, [Ln(hfac) 3 (NITPh-Pa) 2 ][0.5CH 3 (CH 2 ) 5 CH 3 ] (Ln = Gd( 1 ), Tb( 2 ), Dy( 3 ), Ho( 4 ), hfac = hexafluoroacetylacetonate, NITPh-Pa = 2-(3′,4′-dioxylmethylene-phenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide), have been synthesized. The X-ray crystal structure analysis revealed that four compounds have similar mononuclear tri-spin structures, in which the Ln(III) ions are eight-coordinated by two nitronyl nitroxide radicals and three hexafluoroacetylacetonate ligands to form a slightly distorted dodecahedron. In complexes 1 – 4 , isolated mononuclear molecules connect each other through intermolecular hydrogen bonds to form 3D supermolecular framework. Magnetic investigation indicates there are ferromagnetic interactions between Gd(III) ions and radicals in complex 1 . Alternating current(ac) magnetic susceptibilities of complexes 2 and 3 show that there are no non-zero out-of-phase signal, which indicates the inexistence of slow magnetic relaxation. The luminescence properties of complex 2 exhibit the characteristic emission peaks of Tb 3+ ions and the potential for recognition of Cr 2 O 7 2− and Cr 3+ ions. Furthermore, nearly linear at low concentration and the low detection limit (0.01 μM) indicate that complex 2 may potentially be acted as luminescence-based sensor for quantitative and highly sensitive detection of Cr 2 O 7 2− ion. [ABSTRACT FROM AUTHOR]
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Abstract:Four new rare-earth nitronyl nitroxide radical complexes, [Ln(hfac) 3 (NITPh-Pa) 2 ][0.5CH 3 (CH 2 ) 5 CH 3 ] (Ln = Gd( 1 ), Tb( 2 ), Dy( 3 ), Ho( 4 ), hfac = hexafluoroacetylacetonate, NITPh-Pa = 2-(3′,4′-dioxylmethylene-phenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide), have been synthesized. The X-ray crystal structure analysis revealed that four compounds have similar mononuclear tri-spin structures, in which the Ln(III) ions are eight-coordinated by two nitronyl nitroxide radicals and three hexafluoroacetylacetonate ligands to form a slightly distorted dodecahedron. In complexes 1 – 4 , isolated mononuclear molecules connect each other through intermolecular hydrogen bonds to form 3D supermolecular framework. Magnetic investigation indicates there are ferromagnetic interactions between Gd(III) ions and radicals in complex 1 . Alternating current(ac) magnetic susceptibilities of complexes 2 and 3 show that there are no non-zero out-of-phase signal, which indicates the inexistence of slow magnetic relaxation. The luminescence properties of complex 2 exhibit the characteristic emission peaks of Tb 3+ ions and the potential for recognition of Cr 2 O 7 2− and Cr 3+ ions. Furthermore, nearly linear at low concentration and the low detection limit (0.01 μM) indicate that complex 2 may potentially be acted as luminescence-based sensor for quantitative and highly sensitive detection of Cr 2 O 7 2− ion. [ABSTRACT FROM AUTHOR]
ISSN:02775387
DOI:10.1016/j.poly.2017.12.030