Two new nitronyl nitroxide Cu(II) complexes {[Cu(hfac)2]2(NIT-4PyPh)}2(1) and [Cu(hfac)2][(NIT-3PyPh)2](2)(NIT-4PyPh=2-[4-(4-pyridinylmethoxy)
phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide,NIT-3PyPh=2-[4-(3-pyridinylmethoxy)phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide,hfac=hexafluoroacetylacetone), have been synthesized and characterized. The X-ray crystal structure analyses show that structures of the two complexes are different. Complex 1 crystallizes in cyclic metal-radical dimer consisting of four Cu(hfac)2 and two NIT-4PyPh ligands; four Cu(II) atoms adopt two coordinated modes. In the ring, each Cu(II) ion is hexa-coordinated by four oxygen atoms of two hfac ligands and one oxygen atom (ONCNO) and one nitrogen atom of the pyridinyl group from two different radicals. Outside the ring, each Cu(II) is penta-coordinated by four oxygen atoms of two hfac ligands and one oxygen atom (ONCNO) from the radical ligand. Complex 2 crystallizes in discrete molecule, while the Cu(II) atom is hexa-coordinated by four oxygen atoms of two hfac molecules and two nitrogen atoms of the pyridinyl group from two radical ligands.
References
[1]
Ratera, I. and Vecian, J. (2012) Playing with Organic Radicals as Building Blocks for Functional Molecular Materials. Chemical Society Reviews, 41, 303-349. https://doi.org/10.1039/C1CS15165G
[2]
Meng, X.X., Shi, W. and Cheng, P. (2019) Magnetism in One-Dimensional Metal-Nitronyl Nitroxide Radical System. Coordination Chemistry Reviews, 378, 134-150. https://doi.org/10.1016/j.ccr.2018.02.002
[3]
Train, C., Norel, L. and Baumgarten, M. (2009) Organic Radicals, a Promising Route towards Original Molecule-Based Magnetic Materials. Coordination Chemistry Reviews, 253, 2342-2351. https://doi.org/10.1016/j.ccr.2008.10.004
[4]
Sherstobitova, T., Maryunina, K., Tolstikov, S., Letyagin, G., Romanenko, G., Nishihara, S. and Inoue, K. (2019) Ligand Structure Effects on Molecular Assembly and Magnetic Properties of Copper(II) Complexes with 3-Pyridyl-Substituted Nitronyl Nitroxide Derivatives. ACS Omega, 4, 17160-17170. https://doi.org/10.1021/acsomega.9b01575
[5]
Shi, J.Y., Ma, Z.L., Wang, M.C. and Tian, L. (2021) A Family of 2p-3d Complexes Based on 4,5-Dimethyltriazole Nitronyl Nitroxide Radical: Synthesis, Structure, and Magnetic Properties. Inorganica Chimica Acta, 516, 120-122. https://doi.org/10.1016/j.ica.2020.120122
[6]
Sun, J., Wang, K., Jing, P., Lu, J. and Li, L.C. (2019) 2p-3d-4f Heterotrispin Chains and Ring-Chains Bridged by a Nitronyl Nitroxide Ligand: Structure and Magnetic Properties. Crystal Growth & Design, 19, 3576-3583. https://doi.org/10.1021/acs.cgd.9b00489
Calancea, S., Carrella, L., Mocanu, T., Sadohin, V., Raduca, M., Gutu, L., Rocha, J.C., Vaz, M.G.F., Rentschler, E. and Andruh, M. (2021) Magnetic Molecular Rectangles Constructed from Functionalized Nitronyl-Nitroxide Ligands and Lanthanide(III) Ions. Chemistry Europe, 2021, 567-577. https://doi.org/10.1002/ejic.202000954
[9]
Gao, Y.L. and Inoue, K. (2020) Synthesis, Crystal Structures and Magnetic Properties of Nitronyl Nitroxide Radical-Coordinated Copper(II) Complexes. Transition Metal Chemistry, 45, 195-201. https://doi.org/10.1007/s11243-019-00370-y
[10]
Yang, M., Xie, S.F., Liang, X.H., Zhang, Y.D. and Dong, W. (2019) A Novel Nitronyl Nitroxide and Its Copper Complexes: Synthesis, Structures and Magnetic Properties. Inorganica Chimica Acta, 486,589-593. https://doi.org/10.1016/j.ica.2018.10.031
[11]
Zhu, M., Yang, M., Wang, J.J., Li, H.D. and Li, L.C. (2016) Structural and Magnetic Properties of 2p-3d-4f Hetero-Tri-Spin Chains Comprising [{Cu(hfac)2-Radical}2] Dimers and Ln(hfac)3 (hfac=hexafluoroacetylacetonate). Chemistry: An Asian Journal, 11, 1900-1905. https://doi.org/10.1002/asia.201600383
[12]
Ullman, E.F., Call, L. and Osiecki, J.H. (1970) Stable Free Radicals. VIII. New Imino, Amidino, and Carbamoyl Nitroxides. The Journal of Organic Chemistry, 35, 3623-3631. https://doi.org/10.1021/jo00836a008
[13]
Sheldrick, G.M. (1997) SHELXS-97, Program for Crystal Structure Solution. University of Göttingen, Germany.
[14]
Wang, X.F., Hu, P., Li, L.C. and Sutter, J.P. (2015) [(Cu-Radical)2 Ln]: Structure and Magnetic Properties of a Hetero-Trispin Chain of Rings (Ln = YIII, GdIII, TbIII, DyIII). Inorganic Chemistry, 54, 9664-9669. https://doi.org/10.1021/acs.inorgchem.5b01761