Tetranuclear Nickel and Cobalt Complexes with an Incomplete Double-Cubane Structure – Homo- and Heterometallic Complexes and Their 1D Coordination Polymers

Nakajima T, Seto K, Scheurer A, Kure B, Kajiwara T, Tanase T, Mikuriya M, Sakiyama H (2014)

Publication Language: English

Publication Type: Journal article, Report

Publication year: 2014

Journal

European Journal of Inorganic Chemistry Wiley-VCH Verlag

Publisher: Wiley-VCH Verlag

Pages Range: 5021–5033

Journal Issue: 29

URI: http://onlinelibrary.wiley.com/doi/10.1002/ejic.201402536/abstract;jsessionid=E7245E43CE76261F5D1D9834096ECB7D.f03t04

DOI: 10.1002/ejic.201402536

Abstract

The reactions of M(OAc)2·4H2O (M = Ni, Co) with three unsymmetrical amine-diol ligands RN(CH2CH2OH)(CH2CH2CH2OH) (H2Ln: n = 1, R = benzyl; n = 2, R = 4-methylbenzyl; n = 3, R = 2-naphthalenylmethyl) in the presence of NEt3 or pyridine in MeOH or BnOH gave the tetranuclear complexes [M4(HLn)2(OAc)6(MeOH)2] {M = Ni, n = 1 (1a), 2 (1b), 3 (1c); M = Co, n = 1 (4a), 2 (4b), 3 (4c)} and [M4(HLn)2(OAc)6(BnOH)2] {M = Ni, n = 1 (2a), 2 (2b), 3 (2c); M = Co, n = 1 (5a), 2 (5b), 3 (5c)}. When p-xylene-α,α′-diol was used instead of monoalcohols, the tetranuclear {M4O6} units were linked by p-xylene-α,α′-diol to form the 1D coordination polymers [M4(HLn)2(OAc)6(p-HOCH2C6H4CH2OH)]m {M = Ni, n = 1 (3a), 2 (3b); M = Co, n = 1 (6a), 2 (6b)}. The structures of 1–6 were determined by X-ray crystallography and consist of centrosymmetrical tetranuclear {M4O6} face-shared defective double-cubane cores supported by two monodeprotonated (HLn)– ligands. The mixed-metal tetranuclear complexes [Ni2.2Co1.8(HL1)2(OAc)6(MeOH)2] (7) and [Mn1.7Ni2.3(HL1)2(OAc)5(OMe)2] (8) were also synthesized by using equimolar amounts of Ni2+ and M2+ (M = Co, Mn) ions. X-ray crystallographic and fluorescent analyses revealed that 7 is isomorphous with 1a and 4a and contains nonstoichiometric amounts of disordered Ni2+ and Co2+ ions in an average ratio of 2.2:1.8 with different occupancies for the two crystallographically independent metal centers. In contrast, 8 consists of a C2-symmetrical face-shared defective double-cubane {MII3MnIIIO6} core with a Ni/Mn ratio of 2.3:1.7; the amounts of Ni2+ and Mn2+ ions vary depending on the metal sites, and one of the C2 axial positions is exclusively occupied by Mn3+ ions. Detailed magnetostructural analyses on the nickel (1a, 2a, 3a) and cobalt (4a) complexes with appropriate spin-Hamiltonian models showed that both ferro- and antiferromagnetic spin exchange interactions were involved within the tetranuclear units, and their extent depends on the combination of the metal ions and the ligand systems in a delicate fashion.

Authors with CRIS profile

Andreas Scheurer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Nara Women's University / 奈良女子大学 JP Japan (JP) Kwansei Gakuin University / 関西学院大学 (Kangaku / 関学) JP Japan (JP) Yamagata University (YU) JP Japan (JP)

How to cite

APA:

Nakajima, T., Seto, K., Scheurer, A., Kure, B., Kajiwara, T., Tanase, T.,... Sakiyama, H. (2014). Tetranuclear Nickel and Cobalt Complexes with an Incomplete Double-Cubane Structure – Homo- and Heterometallic Complexes and Their 1D Coordination Polymers. European Journal of Inorganic Chemistry, 29, 5021–5033. https://dx.doi.org/10.1002/ejic.201402536

MLA:

Nakajima, Takayuki, et al. "Tetranuclear Nickel and Cobalt Complexes with an Incomplete Double-Cubane Structure – Homo- and Heterometallic Complexes and Their 1D Coordination Polymers." European Journal of Inorganic Chemistry 29 (2014): 5021–5033.

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