Oligonuclear Cobalt Assembly with Schiff-base Ligands
DOI:
https://doi.org/10.26877/asset.v8i2.2730Keywords:
crystal structures, coordination chemistry, cobalt complexes, oligonuclear complexes, Schiff baseAbstract
In order to develop molecular magnetic compounds, oligonuclear cobalt complexes with Schiff-base ligands, 1,3-bis(salicylideneamino)-2-propanol (H3salpr), 1,3-bis(5-chlorosalicylideneamino)-2-propanol (H3clsalpr), 1,3-bis(5-bromosalicylideneamino)-2-propanol (H3brsalpr), and 1,3-bis(5-nitrosalicylideneamino)-2-propanol (H3pnsalpr), were synthesized by reaction of cobalt(II) acetate and Schiff-base ligand in organic solvent. The molecular structures of [CoII{CoIII(µ-HL)(µ-CH3COO)(CH3COO)}2] (HL = Hsalpr and Hbrsalpr), [CoII{CoII(µ-Hsalpr)(µ-CH3COO)}2], and [CoIII2CoII4(µ-L)2(µ3-CH3O)2(µ-CH3O)6(CH3OH)2] (L = salpr, clsalpr, brsalpr, and pnsalpr) were elucidated by the single-crystal X-ray crystallography. The electronic spectra and magnetic susceptibilities with variable-temperature are in accordance with the trinuclear and hexanuclear molecular structures. The cyclic voltammograms are basically featureless, giving a clue to isolate reduced complexes [CoII{CoII(µ-Hsalpr)(µ-CH3COO)}2] and [CoII2(Hpnsalpr)2(CH3OH)]. These findings may guide future design of molecular magnet materials.
References
[1] M. Calligaris, G. Nardin, and L. Randaccio, “Structural Aspects of Metal Complexes with Some Tetradentate Schiff Bases,” Coord. Chem. Rev., vol. 7, pp. 385-403, 1972, DOI : 10.1016/S0010-8545(00)80018-1
[2] P. A. Vigato and S. Tamburimi, “The challenge of cyclic and acyclic schiff bases and related derivatives,” Coord. Chem. Rev., vol. 248, pp.1717-2128, 2004, DOI : 1016/j.cct.2003.09.003
[3] W. Radecka-Paryzek, V. Patroniak, and J. Lisowski, “Metal complexes of polyaza and polyoxaaza Schiff base Macrocycles,” Coord. Chem. Rev., vol. 249, pp.2156-2175, 2005, DOI : 10.1016.j.ccr.2005.02.021
[4] R. Hernandez-Molina and A. Mederos, “Acyclic and Macrocyclic Schiff Base Ligands,” in Comprehensive Coordination Chemistry II, J. A. McCleverty, T. J. Meyer, Ed., Oxford, UK: Elsevier, 2004, pp. 411-446.
[5] M. K. Stern and J. T. Groves, “Oxygen Transfer Reactions of Oxo-Manganese Porphyrins,” in Manganese Redox Enzymes, New York, USA:VCH, 1992, pp. 233-259, ISBN 0-89573-729-9.
[6] T. Katsuki, “Catalytic asymmetric oxidations using optically active (salen)manganese(III) complexes as catalysts,” Coord. Chem. Rev., vol. 140, pp.189-214, 1995, DOI : 10.1016/0010-8545(94)01124-T
[7] P. G. Cozzi, “Metal-Salen Schiff base complexes in catalysis : practical aspects,” Chem. Soc. Rev., vol. 33, pp. 410-421, 2004, DOI : 10.1039/B307853C
[8] K. C. Gupta and A. K. Sutar, “Catalytic activities of Schiff base transition metal complexes,” Coord. Chem. Rev., vol. 252, pp. 1420-1450, 2008, DOI : 10.1016/j.ccr.2007.09.005
[9] P. Das and W. Linert, “Schiff base-derived homogeneous and heterogeneous palladium catalysts for the Suzuki-Miyaura reaction,” Coord. Chem. Rev., vol. 311, pp. 1-23, 2016, DOI : 10.1016/j.ccr.2015.11.010
[10] M. T. Kaczmarek, M. Zabiszak, M. Nowak, and R. Jastrzab, “Lanthanides: Schiff base complexes, applications in cancer diagnosis, therapy, and antibacterial activity,” Coord. Chem. Rev., vol. 370, pp. 42-54, 2018, DOI : 10.1016/j/ccr.2018.05.012
[11] J. Lewinski and D. Prochowicz, “Assemblies Based on Schiff Base Chemistry,” in Comprehensive Supramolecular Chemistry II, vol. 6, pp. 279-304, 2017, DOI : 10.1016/B978-0-12-409547-2.12591-0
[12] J. Rakhtshah, “A comprehensive review on the synthesis, characterization, and catalytic application of transition-metal Schiff-base complexes immobilized on magnetic Fe3O4 nanoparticles,” Coord. Chem. Rev., vol. 467, p. 214614, 2022, DOI : 10.1016/j.ccr.2022.214614
[13] M. Andruh, “The exceptionally rich coordination chemistry generated by Schiff-base ligands derived from o-nanilin,” Dalton Trans, vol. 44, pp. 16633-16653, 2015, DOI : 10.1039/C5DT02661J
[14] T. Tsumaki, “Nebenvalenzringverbidungen. IV. Über einige innerkomplexe Kobaltsalze der Oxyaldimine,” Bull. Chem. Soc. Jpn., vol. 13, pp. 252-260, 1938, DOI : 10.1246/bcsj.13.252
[15] M. Calvin, R. H. Balles, and W. K. Wilmarth, J. Am. Chem. Soc., vol. 68, pp.2254-2256, 1946, DOI : 10.1021/ja01215a041
[16] A. E. Martell and M. Calvin, Chemistry of the Metal Chelate Compounds, Englewood Cliffs, USA: Prentice-Hall, p. 337, 1952.
[17] W. Mazurek, B. J. Kennedy, K. S. Murray, M. J. O’Connor, J. R. Rodgers, M. R. Snow, A. G. Wedd, and P. R. Zwack, “Magnetic Interact ion in Metal Complexes of Binucleating Ligands. 2. Synthesis and Properties of Binuclear Copper(II) Compounds Containing Exogenous Ligands That Bridge through Two Atoms. Crystal and Molecular Structure of a Binuclear µ-Pyrazolato-N,N’-Bridged Dicopper(II) Complex of 1,3-Bis(salicylideneamino)propan-2-ol,” Inorg. Chem., vol. 24, pp. 3258-3264, 1985, DOI : 10.1021/ic00214a033
[18] R. J. Butcher, G. Diven, G. Erickson, G. M. Mockler, and E. Sinn, “Copper Complexes of Binucleating N,N’-Hydroxyalkyldiaminebis(salicylidine) Ligands containing a Cu-O-Cu Bridge and an Exogenous Bridge,” Inorg. Chim. Acta, vol. 111, pp. L55-L56, 1986, DOI : 10.1016/50020-1693(00)84634-4
[19] Y. Nishida and S. Kida, “An Important Factor Determining the Significant Difference in Antiferromagnetic Interactions between Two Homologous (µ-Alkoxo)(µ-pyrazolato-N,N’)dicopper(II) Complexes,” Inorg. Chem., vol. 27, pp. 447-452, 1988, DOI : 10.1021/ic00276a004
[20] M. Mikuriya, T. Sasaki, A. Anjiki, S. Ikenoue, and T. Tokii, “Binuclear Nickel(II) Complexes of Schiff Bases Derived from Salicylaldehydes and 1,n-Diamino-n’-hydroxyalkanes (n,n’=3,2; 4,2; and 5,3) Having an Endogenous Alkoxo Bridge and a Pyrazolato Exogenous Bridge, Bull. Chem. Soc. Jpn., vol. 65, pp. 334-339, 1992, DOI : 10.1246/bcsj.65.334
[21] K. Bertoncello, G. D. Fallon, K. S. Murray, and E. R. T. Tiekink, “Manganese(III) Complexes of a Binucleating Schiff-Base Ligand Based on the 1,3-Diaminopropan-2-ol Backbone,” Inorg. Chem., vol. 30, pp. 3562-3568, 1991, DOI : 10.1021/ic00018a033
[22] M. Mikuriya, Y. Yamato, and T. Tokii, “1,3-Bis(salicylideneamino)-2-propanol as the Ligand for Manganese(III) Ions,” Bull. Chem. Soc. Jpn., vol. 65, pp. 1466-1468, 1992, DOI : 10.1246/bcsj.65.1466
[23] A. Gelasco and V. L. Pecoraro, “[Mn(III)(2-OHsalpn)]2 Is an Efficient Functional Model for the Manganese Catalases,” J. Am. Chem. Soc., vol. 115, pp. 7928-7929, 1993, DOI : 10.1021/ja00070a069
[24] A. Gelasco, M. L. Kirk, J. W. Kampf, and V. L. Pecoraro, “The [Mn2(2-OHsalpn)2]2–,–,0,+ System: Synthesis, Structure, Spectroscopy, and Magnetism of the First Structurally Characterized Dinuclear Manganese Series Containing Four Distinct Oxidation States,” Inorg. Chem., vol. 36, pp. 1829-1837, 1997, DOI : 10.1021/ic970140i
[25] J. A. Bonadies, M. L. Kirk, M. S. Lah, D. P. Kessissoglou, W. E. Hatfield, and V. L. Pecoraro, “Structurally Diverse Manganese(III) Schiff Base Complexes: Chains, Dimers, and Cages,” Inorg. Chem., vol. 28, pp. 2037-2044, 1989, DOI : 10.1021/ic00310a008
[26] Y.-Y. Kou, Q. Zhao, X.-R. Wang, M. L. Li, and X.-H. Ren, “Synthesis of three binuclear Mn complexes: Characterization and DNA binding and Cleavage properties,” J. Coord. Chem., vol. 72, pp. 2393-2408, 2019, DOI : 10.1080/00958972.2019.1647339
[27] M. Mikuriya, Y. Koyama, D. Yoshioka, and R. Mitsuhashi, “Dinuclear Manganese(III) Complex with a Schiff-base Having a Di-µ-acetato-µ-alkoxido-bridged Core,” X-ray Struct. Anal. Online, vol. 36, pp.7-9, 2020, DOI : 10.2116/xraystruct.36.7
[28] Y. Lan, G. Novitchi, R. Clerac, J.-K. Tang, N. T. Madhu, I. J. Hewitt, C. E. Anson, S. Brooker, and A. Powell, “Di-, tetra- and hexanuclear iron(III), manganese(II/III) and copper(II) complexes of Schiff-base ligands derived from 6-substituted-2-formylphenols,” Dalton Trans., vol. 38, 1721-1727, 2009, DOI : 10.1039/b818113f
[29] M. Mikuriya, Y. Naka, D. Yoshioka, and M. Handa, “Synthesis and Crystal Structures of Dinuclear Cobalt(III) Complexes with 1,3-Bis(5-nitrosalicylideneamino)-2-propanol and 1,3-Bis(3-nitrosalicylideneamino)-2-propanol,” X-ray Struct. Anal. Online, vol. 32, pp. 55-58, 2016, DOI : 10.2116/xraystruct.32.55
[30] H. Liang, X.-J. Wang, Y.-L. Cong, S.-T. Li, and J.-Q. Zeng, ”Synthesis and Crystal Structure of Schiff Base N,N’-Bis(2-Hydroxybenzylidene)-2-Hydroxy-1,3-propanediamine,” Jiegou Huaxue Chin. J. Struct. Chem., vol. 16, pp.141-143, 1997,
[31] A. Elmali, “Conformation and structure of 1,3-bis(2-hydroxy-5-bromosalicylideneamine)propan-2-ol,” J. Chem. Crystallogr., vol. 30, pp. 473-477, 2000, 10. DOI : 10.1023/A:1011355601133
[32] M. Mikuriya, Y. Naka, and D. Yoshioka, “Synthesis and Crystal Structure of 1,3-Bis(5-nitrosalicylideneamino)-2-propanol,” X-ray Struct. Anal. Online, vol. 31, pp.55-56, 2015, DOI : 10.2116/xraystruct.31.55; Erratum: X-ray Struct. Anal. Online, vol. 32, pp.11, 2016, DOI : 10.2116/xraystruct.32.11
[33] M. Mikuriya, Y. Koyama, and R. Mitsuhashi, “Synthesis and Crystal Structure of 1,3-Bis(5-chloro-3-methoxysalicylideneamino)-2-propanol Trihydrate,” X-ray Struct. Anal. Online, vol. 35, pp.33-34, 2019, DOI : 10.2116/xraystruct.35.33
[34] W. Su, D. Tian, Z. Yu, L. Yang, and Y. Niu, “Crystal structure of 2-ethoxy-6-((E)-3-ethoxy-2-hydroxybenzilidene)amino)-2-hydroxypropyl)imino)methyl)phenolate, C21H26N2O5,” Zeitschrift fur Lristallographie New Cryst. Struct., vol. 235, pp. 53-54, 2020, DOI : 10.1515/ncrs-2019-0468
[35] M. Mikuriya, N. Tsuchimoto, Y. Koyama, R. Mitsuhashi, and M. Tsuboi, “Crystal Structure of 1,3-Bis(3,5- dibromosalicylideneamino)-2-propanol,” X-ray Struct. Anal. Online, vol. 38, pp.3-5, 2022, DOI : 10.2116/xraystruct.38.3
[36] S. Banerjee, M. Nandy, S. Sen, S. Mandal, G. M. Rosair, A. M. Z. Slawin, C. J. G. Garcia, J. M. Clemente-Juan, E. Zangrando, and N. Guidolin, “Isolation of four new CoII/CoIII and NiII complexes with a pentadentadentate Schiff base ligand: Synthesis, structural descriptions and magnetic studies,” Dalton Trans., vol. 40, pp. 1652-1661, 2011, DOI : 10.1039/c0dt00923g
[37] K. Das, C. Massera, E. Garribba, and A. Frontera, “Synthesis, structural and DFT interpretation of a Schiff base assisted Mn(III) derivative,” J, Mol. Struct., vol. 1199, p. 126985, 2020, DOI : 10.1016/j.molstruc.2019.126985
[38] D. Martinez, M. Motevalli, and M. Watkinson, “Is there really a diagnostically useful relationship between the carbon-oxygen stretching frequencies in metal carboxylate complexes and their coordination mode?,” Daltron Trans., vol. 39, pp. 446-455, 2010, DOI : 10.1039/b913865j
[39] J. P. Grundhoefer, E. E. Hardy, M. M. West, A. B. Curtiss, and A. E. V. Gorden, “Mononuclear Cu(II) and Ni(II) complexes of bis(naphthalen-2-ol) Schiff base ligands,” Inorg. Chim. Acta, vol. 484, pp. 125-132, 2019, DOI : 10.1016/j.ica.2018.09.043
[40] E. Donmez, H. Kara, A. Karakas, H. Unver, and A. Elmali, “Synthesis, molecular structure, spectroscopic studies and second-order nonlinear optical behavior of N,N’-(2-hydroxy-propane-1,3-diyl)-bis(5-nitrosalicylideneaminato-N,O)-copper(II),” Spectrochim. Acta, vol. A66, pp.1141-1146, 2007, DOI : 10.1016/j.saa.2006.05.027
[41] M. T. Kaczmarek, M. Skrobanska, M. Zabiszak, M. Walesa-Chorab, M. Kubicki, and R. Jastrzab, “Coordination properties of N,N’-bis(5-methylsalicylidene)-2-hydroxy-1,3-propanediamine with d- and f-electron ions: Crystal structure, stability in solution, spectroscopic and spectroelectrochemical studies,” RSC Adv., vol. 8, pp. 30994-31007, 2018, DOI : 10.1039/c8ra03565b
[42] M. Azam, Z. Hussain, I. Warad, S. Al-Resayes, M. S. Khan, A. Trzesowska-Kruszynska, and R. Kruszynski, ”Novel Pd(II)-salen complexes showing high in vitro anti-proliferative effects against human heptatoma cancer by modulatingn, specific regulatory genes,” Dalton Trans., vol. 41, pp. 10854-10864, 2012, DOI : 10.1039/c2dt31143g
[43] M. Mikuriya, N. Tsuchimoto, Y. Koyama, R. Mitsuhashi, and M. Tsuboi, “Crystal Structure of a Hydrolyzed Product of the Cobalt(III) Complex with 1-(3,5-Dichlorosalicylideneamino)-3-amino-2-propanol,” X-ray Struct. Anal. Online, vol. 38, pp.9-11, 2022, DOI : 10.2116/xraystruct.38.9
[44] E. Baca-Solis, S. Bernes, H. Vazquez-Lima, M.-E. Boulton, R. E. P. Winpenny, and Y. Reyes-Ortega, “Synthesis, Electronic, Magnetic and Structural Characterization of New Trinuclear Mixed-Valence CoIII-CoII-CoIII Complex,” ChemistrySelect, vol. 1, pp. 6866-6871, 2016, DOI : 10.1002/slct.201601648
[45] M. Mikuriya, Y. Naka, A. Inaoka, M. Okayama, D. Yoshioka, H. Sakiyama, M. Handa, and M. Tsuboi, “Mixed-Valent Trinuclear CoIII-CoII-CoIII Complex with 1,3-Bis(5-chlorosalicylideneamino)-2-propanol,” Molecules, vol. 27, p. 4211, 2022, DOI : 10.3390/molecules27134211
[46] M. Dieng, I. Thiam, M. Gaye, A. S. Sall, and A. H. Barry, “Synthesis, Crystal Structures and Spectroscopic Properties of a Trinuclear [Cu3(HL)2(NO3)2](H2O)(CH3CH2OH) Complex and a [Mn(HL)(CH3COOH)]n Polymer With H3L=N, N’-(2-hydroxypropane-1,3-dihyl)-bis-(salicylaldimine),” Acta Chim. Slov., vol. 53, pp. 417-423, 2006.
[47] D. Dey, G. Kaur, M. Patra, A. R. Choudhury, N. Kole, and B. Biswas, “A perfectly linear trinuclear zinc-Schiff base complex: Synthesis, luminescence property and photocatalytic activity of zinc oxide nanoparticle,” Inorg. Chim. Acta, vol. 421, pp. 335-341, 2014, DOI : 10.1016/j.ica.2014.06.014
[48] J. Jiang, D.-Y. Zhang, J.J. Suo, W. Gu, J.-L. Tian, X. Liu, and S.-P. Yan, “Synthesis, magnetism and spectral studies of six defective dicubane tetranuclear {M4O6} (M = NiII, CoII, ZnII) and three trinuclear CdII complexes with polydentate Schiff base ligands,” Dalton Trans., vol. 45, pp. 10233-10248, 2016, DOI : 10.1039/c6dt00380j
[49] R. Bagai, K. A. Abboud, and G. Christou, “Ligand-induced distortion of a tetranuclear manganese butterfly complex,” Dalton Trans., vol. 35, pp. 3306-3312, 2006, DOI : 10.1039/b602192a
[50] M. Mikuriya, S. Kudo, C. Matsumoto, S. Kurahashi, S. Tomohara, Y. Koyama, D. Yoshioka, and R. Mitsuhashi, “Mixed-valent tetranuclear manganese complexes with pentadentate Schiff-base ligand having a Y-shaped core,” Chem. Pap., vol. 72, pp. 853-862, 2018, DOI : 10.1007/s11696-017-0305-6
[51] M. Mikuriya, S. Kurahashi, S. Tomohara, Y. Koyama, D. Yoshioka, R. Mitsuhashi, and H. Sakiyama, “Synthesis, Crystal Structures, and Magnetic Properties of Mixed-Valent Tetranuclear Complexes with Y-Shaped MnII2MnIII2 Core,” Magnetochemistry, vol. 5, p. 8, 2019, DOI : 10.3390/magnetochemistry5010008
[52] Y.-Y. Kou, M.-L. Li, and X.-H. Ren, “Synthesis, structure, and DNA binding/cleavage of two novel binuclear Co(II) complexes,” Spectrochim. Acta, vol. A205, pp. 435-441, 2018, DOI : 10.1016/j.saa.2018.07.050
[53] M. Mikuriya, S. Ikenoue, R. Nukada, and J.-W. Lim, “Synthesis and Structural Characterization of Tetranuclear Zinc(II) Complexes with a Linear Array,” Bull. Chem. Soc. Jpn., vol. 74, pp. 101-102, 2001, DOI : 10.1246/bcsj.74.101
[54] F.-L. Yang, F. Shao, G.-Z. Zhu, Y.-H. Shi, F. Gao, and X.-L. Li, “Structures and Magnetostructural Correlation Analyses for Two Novel Hexanuclear Complexes Based on a Pentadentate Schiff Base Ligand,” ChemistrySelect, vol. 2, pp. 110-117, 2017, DOI : 10.1002/slct.201601698
[55] M. Mikuriya, Y. Koyama, C. Kamioka, R. Mitsuhashi, and M. Tsuboi, “Mixed-valent Manganese Complex with a Schiff-base Having a Di-µ4-oxido-di-µ3-oxido-di-µ3-carboxylato-hexa-µ-carboxylato-bridged MnII2MnIII6 Core,” X-ray Struct. Anal. Online, vol. 38, pp.33-35, 2022, DOI : 10.2116/xraystruct.38.33
[56] M. Murrie, “Cobalt(II) single-molecule magnets,” Chem. Soc. Rev., vol. 39, pp.1986-1995, 2010, DOI : 10.1039/B913279C
[57] R. Mitsuhashi, K. S. Pederson, T. Ueda, T. Suzuki, J. Bendix, and M. Mikuriya, “Field-induced single-molecule magnet behvior in ideal trigonal antiprismatic cobalt(II) complexes: precise geometrical control by a hydrogen-bonded rigid metalloligand,” Chem. Commun., vol. 54, pp.8869-8872, 2018, DOI : 10.1039/c8cc04756a
[58] R. Mitsuhashi, S. Hosoya, T. Suzuki, Y. Sunatsuki, H. Sakiyama, and M. Mikuriya, “Hydrogen-bonding interactions and magnetic relaxation dynamics in tetracoordinated cobalt(II) single-ion magnets,” Dalton Trans., vol.48, pp.395-399, 2019, DOI: 10.1039/c8dt04537b
[59] O. Kahn, Molecular Magnetism, Cambridge, UK: VCH, 1993.
[60] G. M. Sheldrick, “A short History of SHELX,” Acta Crystallogr. Sect A, vol.64, pp. 112-122, 2008, DOI : 10.1107/S0108767307043930
[61] M. Mikuriya, “Copper(II) Acetate as a Motif for Metal-Assembles Complexes,” Bull. Jpn. Soc. Coord. Chem., vol. 52, pp.17-28, 2008, DOI : 10.4019/bjscc.52.17
[62] M. Mikuriya, A. Fujita, T. Kotera, D. Yoshioka, H. Sakiyama, M. Handa, and M. Tsuboi, “Synthesis, Crystal Structures, Electronic Spectra, and Magnetic Properties of Bis(µ-Thiolato)-Bridged Trinuclear CoII Complexes with Tridentate-N,N,S-Thiolates,” Advance Sustainable Science, Engineering and Technology (ASSET), vol. 3, no. 1, pp.0210102-01~0210102-13, 2021, DOI : 10.26877/asset.v3i1.8352
[63] R. Grobelny, M. Melnik, and J. Mrozinski, Cobalt Coordination Compounds: Classification and Analysis of Crystallographic and Structural Data, Wroclaw, Poland: Dolnoslaskie Wydawnictwo Edukacyine,1995.
[64] K. Nakanishi, P. H. Solomon, and N. Furutachi, Infrared Absorption Spectroscopy, Tokyo, Japan: Nankodo (in Japanese), 1978.
[65] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B, 6th ed., Hoboken, USA: John Wiley & Sons, 2009, pp. 64-67, ISBN 978-0-471-74493-1.
[66] Y. Murakami and K. Sakata, “Electronic Spectra of Metal Complexes,” in Chelate Chemistry, K. Ueno, Ed., Tokyo, Japan: Nankodo (in Japanese), 1976, vol. 1, pp.91-336.
[67] A. W. Addison, T. N. Rao, J. Reediik, J. van Rijn, and G. C. Verschoor, J. Chem. Soc., Dalton Trans., pp. 1349-1356, 1984, DOI : 10.1039/DT9840001349
Downloads
Published
Issue
Section
License
Copyright (c) 2026 Advance Sustainable Science Engineering and Technology
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.
