A New Quinoxalinyl-Substituted Nitronyl Nitroxide Radical and its Five-Spin CuII and Four-Spin MnII Complexes: Syntheses, Crystal Structures, and Magnetic Properties

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doi:10.1071/CH12077

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Royal Australian
Chemical Institute

A New Quinoxalinyl-Substituted Nitronyl Nitroxide Radical and its Five-Spin Cu^II and Four-Spin Mn^II Complexes: Syntheses, Crystal Structures, and Magnetic Properties

Chao Wang ^A, Yue Ma ^A ^B ^D, Yali Wang ^A, Qinglun Wang ^A, Licun Li ^A, Peng Cheng ^A and Daizheng Liao ^A ^C

^A Department of Chemistry, Nankai University, Tianjin 300071, P. R. China.
^B Tianjin Key Lab on Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300071, P. R. China.
^C State Key Laboratory of Physical Chemistry of Solid Surface, Xiamen University, Xiamen 361005, P. R. China.
^D Corresponding author. Email: maynk@nankai.edu.cn

Australian Journal of Chemistry 65(6) 672-679 http://dx.doi.org/10.1071/CH12077
Submitted: 5 February 2012 Accepted: 20 March 2012 Published: 3 May 2012





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Abstract

A new radical of QNXL-2NIT (1) (QNXL-2NIT = 2-(2-quinoxalinyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) and its complexes [Cu(hfac)₂]₃(QNXL-2NIT)₂·2CHCl₃ (2) and [Mn(hfac)₂]₂(QNXL-2NIT)₂ (3) (hfac = 1,1,1,5,5,5-hexfluoroacetylacetone) were first reasonably designed and synthesised in this paper. The X-ray structure determination revealed that by introducing the quinoxalinyl ring group to the nitronyl nitroxide radical, QNXL-2NIT affords more coordination sites for metal ions. We successfully obtained its copper complex with linear tri-nuclear five-spin structure. However, when we substituted Mn^II as the central metal, complex 3 exhibits a rectangle-like four-spin framework containing two Mn^II ions and two radicals in one molecule. The magnetic study of the two complexes shows that there are strong antiferromagnetic interactions between the radical and the terminal Cu^II ions with g = 2.25, J = –291.67 cm^–1 and zJ′ = –0.25 cm^–1 and the dominating interactions between the Mn^II ion and the radical in complex 3 are also antiferromagnetic with the parameters of g = 1.99, J ₁ = –77.00 cm^–1 and J ₂ = 0.34 cm^–1.

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