Citation: Xun FENG, Haipeng FANG, Yang AN, Ce ZHANG, Xueyi CHEN, Bowen GUO. Crystal structures and magnetic properties of manganese and cobalt binuclear complexes based on nitroxide radical[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(2): 421-429. doi: 10.11862/CJIC.20230277 shu

Crystal structures and magnetic properties of manganese and cobalt binuclear complexes based on nitroxide radical

Xun FENG ^1,, ,
Haipeng FANG ¹ ,
Yang AN ¹ ,
Ce ZHANG ¹ ,
Xueyi CHEN ² ,
Bowen GUO ³

1.
College of Chemistry and Chemical Engineering and Henan Key Laboratory of Function Oriented Porous Materials, Luoyang Normal University, Luoyang, Henan 471934, China
2.
Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China
3.
College of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang, Henan 473601, China

Corresponding author: Xun FENG, fengx@lynu.edu.cn
Received Date: 26 July 2023
Revised Date: 10 December 2023

Figures(5)

Two analogous binuclear coordination complexes derived from nitronyl nitroxide radical ligands have been synthesized. Their general formulae are [Mn₂(hfac)₄(NIT-mo-pmy)₂] (1) and [Co₂(hfac)₄(NIT-mo-pmy)₂] (2), respectively, where hfac=hexafluoroacetylacetone and NIT-mo-pmy=2-(2-methoxy-5′-pyrimidinyl)-4,4,5,5-tetra-methyl-imidazoline-3-oxy-1-oxyl radical. Both complexes crystallize in a triclinic system P1 space group, exhibiting a centrosymmetric rectangle-like array based on dimer coordination units. Variable-temperature magnetic characterizations reveal the presence of antiferromagnetic exchanges between central ions and nitroxide radicals in both fourspin nitroxide radical complexes. The different strengths of both complexes were investigated based on structure-property relationship analysis. The magnetic behaviors of the Mn (Ⅱ) complex have been quantitatively evaluated through an appropriate magnetic model and were compared with the relevant complexes.
- manganese(Ⅱ) complex,
- cobalt(Ⅱ) complex,
- crystal structure,
- NIT-mo-pmy radical ligand,
- antiferromagnetic interaction
1. [1]
  Tumanov S V, Veber S L, Tolstikov S E, Artiukhova N A, Romanenko G V, Ovcharenko V I, Fedin M V. Light-induced spin state switching and relaxation in spin pairs of copper(Ⅱ)-nitroxide based molecular magnets[J]. Inorg. Chem., 2017,56(19):11729-11737. doi: 10.1021/acs.inorgchem.7b01689
2. [2]
  Gatteschi D, Sessoli R. Quantum tunneling of magnetization and related phenomena in molecular materials[J]. Angew. Chem. Int. Ed., 2003,42(3):268-297. doi: 10.1002/anie.200390099
3. [3]
  Caneschi A, Gatteschi D, Lalioti N, Sangregorio C, Sessoli R, Venturi G, Vindigni A, Rettori A, Pini M G, Novak M A. Cobalt(Ⅱ)-nitronyl nitroxide chains as molecular magnetic nanowires[J]. Angew. Chem. Int. Ed., 2001,40(9):1760-1763. doi: 10.1002/1521-3773(20010504)40:9<1760::AID-ANIE17600>3.0.CO;2-U
4. [4]
  Poneti G, Bernot K, Bogani L, Andrea C, Roberta S, Wolfgang W, Dante G. A rational approach to the modulation of the dynamics of the magnetization in a dysprosium-nitronyl-nitroxide radical complex[J]. Chem. Comm., 2007,18:1807-1809.
5. [5]
  Tretyakov E, Fokin S, Romanenko G, Ikorskii V, Vasilevsky S, Ovcharenko V. 2D and 3D Cu(hfac)₂ complexes with nitronyl nitroxide biradicals[J]. Inorg. Chem., 2006,45(9):3671-3678. doi: 10.1021/ic060132e
6. [6]
  Wang X F, Zhu M, Wang J, Li L C. Unusual Gd nitronyl nitroxide antiferromagnetic coupling and slow magnetic relaxation in the corresponding Tb analogue[J]. Dalton Trans., 2015,44:13890-13894. doi: 10.1039/C5DT01487E
7. [7]
  Zhang J Y, Liu C M, Zhang D Q, Gao S, Zhu D B. Syntheses, crystal structures, and magnetic properties of two cyclic dimer M₂L₂ complexes constructed from a new nitronyl nitroxide ligand and M(hfac)₂ (M=Cu²⁺, Mn²⁺)[J]. Inorg. Chim. Acta, 2007,360(31):3553-3559.
8. [8]
  Luneau D, Risoan G, Rey P, Grand A, Caneschi A, Gatteschi D, Laugier J. Transition metal derivatives of a chelating nitronyl nitroxide ligand. Nickel(Ⅱ) and manganese(Ⅱ) complexes[J]. Inorg. Chem., 1993,32(24):5616-5622. doi: 10.1021/ic00076a032
9. [9]
  Liu X, Feng X, Meihaus K R, Meng X, Zhang Y, Li L, Liu J L, Pedersen K S, Keller L, Shi W, Zhang Y Q, Cheng P, Long J R. Coercive fields above 6 T in two cobalt(Ⅱ)-radical chain compounds[J]. Angew. Chem. Int. Ed., 2020,59(26):10610-10618. doi: 10.1002/anie.202002673
10. [10]
  Okamura Y, Nogami T, Ishida T. The hardest magnet from a coordination polymer of alternating cobalt(Ⅱ)-radical heterospins[J]. Chem. Lett., 2009,38(7):740-741. doi: 10.1246/cl.2009.740
11. [11]
  Sheldrick G M. SHELXL-2014/7, Program for the solution of crystal structure. University of Göttingen, Germany, 2014.
12. [12]
  Sheldrick G M. SHELXL-2014/7, Program for the refinement of crystal structure. University of Göttingen, Germany, 2014.
13. [13]
  Lloret F, Julve M, Cano J, Ruiz G R, Pardo E. Magnetic properties of six-coordinated high-spin cobalt(Ⅱ) complexes: Theoretical background and its application[J]. Inorg. Chem. Acta, 2008,361(12/13):3432-3445.
14. [14]
  Zhu M, Li Y G, Ma Y, Li L C, Liao D Z. Unprecedented nitronyl nitroxide bridged 3d-4f complexes: Structure and magnetic properties[J]. Inorg. Chem., 2013,52(21):12326-12328. doi: 10.1021/ic402241f
15. [15]
  Feng X, Sun Y L, Li R F, Zhang T, Guo N, Wang L Y. Two novel europium coordination polymers based on fluorine substituted and similar carboxylate ligands: Syntheses, structures and luminescence[J]. Inorg. Chem. Commun., 2016,73:190-195. doi: 10.1016/j.inoche.2016.10.003
16. [16]
  Wang Y F, He C J. Syntheses, crystal structures and characterization of two coordination polymers based on mixed ligands[J]. Chin. J. Struct. Chem., 2018,37(3):481-489.
17. [17]
  Wang H M, Liu Z L, Liu C M, Zhang D Q, Lu Z L, Geng H, Shuai Z G, Zhu D B. Coordination complexes of 2-(4-quinolyl) nitronyl nitroxide with M(hfac)₂[M=Mn(Ⅱ), Co(Ⅱ), and Cu(Ⅱ)]: Syntheses, crystal structures, and magnetic characterization[J]. Inorg. Chem., 2004,43(13):4091-4098. doi: 10.1021/ic049946q
18. [18]
  Yu Y X, Hu H M, Zhang D Q, Wang Z Y, Zhu D B. Two new nitronyl nitroxide radicals and their complexes with M(hfac)₂[M=Co(Ⅱ), Ni(Ⅱ), Mn(Ⅱ)]: Syntheses, crystal structures, and magnetic characterizations[J]. Chin. J. Chem., 2007,25(9):1259-1266. doi: 10.1002/cjoc.200790234
19. [19]
  LIU J W, ZHANG J W, GU C S, WANG S. Synthesis, crystal structure and thermal properties of two complexes constructed by 2,2'-dithiosalicylic acid, bis(2-carboxyphenyl)sulfide and N-donor ligands[J]. Chinese J. Inorg. Chem., 2014,30(11):2684-2690.
20. [20]
  Zhou N, Wang Y L, Wang H L, Li W J, Guo Z, Ma Y, Li L C, Wang Q L, Cheng P, Liao D Z. Structural design and magnetic properties study on two nitronyl nitroxide radicals-Mn(Ⅱ) complexes with hetero chain or mononuclear tri-spin structures[J]. Polyhedron, 2015,89:96-100. doi: 10.1016/j.poly.2014.12.032
21. [21]
  Yamase T, Fukaya K, Nojiri H, Ohshima Y. Ferromagnetic exchange interactions for Cu₆¹²⁺ and Mn₆¹²⁺ hexagons sandwiched by two B-α-[XW₉O₃₃]^9- (X=As^Ⅲ and Sb^Ⅲ) ligands in D_3d-symmetric polyoxotungstates[J]. Inorg. Chem., 2006,45(19):7698-7704. doi: 10.1021/ic060666f
22. [22]
  Fegy K, Sanz N, Luneau D, Belorizky E, Re Y P. Proximate nitroxide ligands in the coordination spheres of manganese(Ⅱ) and nickel(Ⅱ) ions. Precursors for high-dimensional molecular magnetic materials[J]. Inorg. Chem., 1998,37(18):4518-4523. doi: 10.1021/ic971618l
23. [23]
  Tian H X, Li Y G, Zhang C M, Mei X L, Hu P, Li L C. Two novel cyclic dimer M₂L₂ complexes constructed from 2‑[(4‑carboxyl) phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3 oxide: Crystal structure and magnetic properties[J]. Polyhedron, 2013,52:1053-1058. doi: 10.1016/j.poly.2012.06.076
24. [24]
  Sun J, Xi L, Xie J, Wang K, Li L C, Sutter J P. A loop chain and a three-dimensional network assembled from a multi-dentate nitronyl nitroxide radical and M(hfac)₂ (M=Co^Ⅱ, Cu^Ⅱ)[J]. Dalton Trans., 2018,47:14630-14635. doi: 10.1039/C8DT03222J
25. [25]
  Ma Y, Zhang J Y, Cheng A L, Sun Q, Gao E Q, Liu C M. Antiferro-and ferromagnetic interactions in Mn(Ⅱ), Co(Ⅱ), and Ni(Ⅱ) compounds with mixed azide-carboxylate bridges[J]. Inorg. Chem., 2009,48(13):6142-6151. doi: 10.1021/ic900472d
26. [26]
  Yang Q, Li X. L, Tang J. Syntheses, structures and magnetic properties of M₂ (M=Fe, Co) complexes with N₆ coordination environment: Field-induced slow magnetic relaxation in Co₂[J]. Magnetochemistry, 2021,7(12):153-158. doi: 10.3390/magnetochemistry7120153
27. [27]
  Kamaal S, Gupta M, Mishra R, Ali A, Alarifi A, Afzal M, Das R, Ahmad M. A three-dimensional pentanuclear Co(Ⅱ) coordination polymer: Structural topology, Hirschfeld surface analysis and magnetic properties[J]. ChemistrySelect, 2020,5(43):13732-13737. doi: 10.1002/slct.202003564
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