Molecular Magnets Based on Nickel(II) Complexes with 3-Imidazoline Nitroxides and Alcohols

Ikorskiǐ, V. N.; Овчаренко, В. И.; Shvedenkov, Yurii G.; Романенко, Г. В.; Fokin, S. V.; Sagdeev, R. Z.

doi:10.1021/ic9801847

Cited by 29 publications

(17 citation statements)

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“…O•−N<} hydrogen bonds with two adjacent {RO H -ML 2-H OR} fragments. As a result, the bridging molecules of alcohols link the {ML 2 } fragments into polymer layers; that is, the 2-D structure is formed by hydrogen bonds, 123,124 which can be treated as a certain analogy to the formation of complex protein structures.…”

Section: Molecular Magnets Based On 2-d Systemsmentioning

confidence: 99%

“…Moreover, the removal of alcohol molecules and a transition to layered polymer molecules in solid M(L n ) 2 leads to the impossibility of ferromagnetic ordering in the latter. 120,123 This is a paradox at first sight because the transition from M(L n ) 2 to M(L n ) 2 (ROH) 2 is actually accompanied by a drastic increase in the fraction of the pure organic component in the compound and a decrease in the number of paramagnetic centers per unit volume of the solid complex. Nevertheless, this increase gives rise to the ability to undergo a magnetic phase transition.…”

Section: Molecular Magnets Based On 2-d Systemsmentioning

confidence: 99%

“…Preliminary modeling showed that polymer layers could remain almost unperturbed and linked through polymethylene chains (-CH 2 -) n , lying between the coordinated hydroxyl groups of alcohols at n = 4 or 5. Indeed, M(L 26 ) 2 (HO(CH 2 ) 4 OH) and M(L 26 ) 2 (HO(CH 2 ) 5 OH) heterospin framework polymers, where M = nickel, cobalt, were also obtained with both 1,4-butanediol and 1,5-pentanediol and were capable of undergoing a magnetic phase transition to the magnetically ordered state at T c ∼4-8 K. 123 It is noteworthy that complexes with bifunctional alcohols possess high kinetic stability. 141 In summary, the data presented in this section show that, due to the high kinetic stability of nitroxides, as well as the unlimited possibilities for their chemical modification and the possibility of changing the coordination mode of radicals due to selective combination of functional groups, the design of molecular magnets based on complexes of paramagnetic metal ions with nitroxides is one of the most effective methods for the preparation of various magnetoactive compounds.…”

Section: Molecular Magnets Based On 3-d Systemsmentioning

confidence: 99%

“…A full-colour version of this figure appears in the Colour Plate section of this book. anisotropy of magnetic properties90,91,123,140,141 and spin density distribution 127,134,142,143. These single crystals are transparent and very beautiful (Figure 13.2).…”

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confidence: 93%

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Metal–Nitroxide Complexes: Synthesis and Magnetostructural Correlations

Овчаренко¹

2010

Stable Radicals

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IntroductionInteractions between the paramagnetic ions of transition metals and stable radicals are convenient and effective methods for the synthesis of multispin molecules. These metal-nitroxide systems are often called heterospin systems because they contain paramagnetic centers with both d (or f) odd electrons and centers with p electrons. Paramagnetic centers can differ in the electron spin, g factor, the character of electron spin density delocalization, and heat capacity. The presence of several paramagnetic centers in heterospin molecules has stirred growing interest in their magnetic properties because these compounds are convenient objects for studying the subtle peculiarities of exchange interactions and revealing valuable magnetostructural correlations. That is why coordination chemistry of transition metals with stable nitroxides is an actively developing direction in modern chemistry that contributes to problem solving in the field of molecular magnetism. The results of studies on the synthesis and properties of metal complexes with nitroxides have been considered from different viewpoints and at different times in many monographs and reviews. 1 -19 Importantly, this approach offers the potential for control over the structure of the designed heterospin molecule and the character of interactions between the odd electrons of paramagnetic centers, which is necessary for constructing justifiable magnetostructural correlations. This is one of the factors responsible for the continuous growth of the number of new metal-nitroxide complexes. The Cambridge Structural Database alone contains more than one thousand structurally defined metal-nitroxide systems. 20 Therefore, currently it is impossible and not necessary to collect all available literature data on the synthesis and properties of metal-nitroxide systems in one publication. In any account, a comprehensive review of this kind will already have become incomplete by the time of its publication because new heterospin compounds based on transition metal compounds with nitroxides are being added daily to the list. However, the Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron CompoundsEdited by Robin G. Hicks

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Section: Molecular Magnets Based On 2-d Systemsmentioning

confidence: 99%

Section: Molecular Magnets Based On 2-d Systemsmentioning

confidence: 99%

Section: Molecular Magnets Based On 3-d Systemsmentioning

confidence: 99%

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Metal–Nitroxide Complexes: Synthesis and Magnetostructural Correlations

Овчаренко¹

2010

Stable Radicals

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“…The KNi 4 Piv 7 (OH) 2 (EtOH) 6 and NiL 2 (HOC 4 H 8 OH) precursors were prepared using the known techniques [4,20]. For I, the synthesis technique was found making it possible to reproducibly obtain the compound in a sufficient amount.…”

Section: Methodsmentioning

confidence: 99%

Crystal structure of polynuclear pivalate Ni(II) complexes with butanediol

et al. 2014

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N‐Alkylimidazol‐5‐yl‐substituted Nitronyl Nitroxides and Their Mononuclear Cu(II) Complexes: Synthesis, Structure and Magnetic Properties

Golomolzina,

Tolstikov,

Smirnova

et al. 2024

Chemistry A European J

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A novel synthetic approach has been employed to synthesize a series of new nitronyl nitroxides: 2‑(1‐propyl‐1H‐imidazol‐5‐yl)‐ (Ln‐Pr), 2‐(1‐isopropyl‐1H‐imidazol‐5‐yl)‐ (Li‐Pr) and 2‐(1‐butyl‐1H‐imidazol‐5‐yl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazole‐3‐oxide‐1‐oxyl (Ln‐Bu). The reaction of Cu(hfac)2 with LR in a 1:2 ratio yields mononuclear heterospin complexes [Cu(hfac)2(LR)2] (LR= Ln‑Pr, Li‑Pr, Ln‐Bu), which have a similar crystal structure to the “jumping” crystals [Cu(hfac)2(LMe)2] that exhibit chemomechanical activity. It was shown that an increase in the alkyl substituent R leads to changes in the crystal packing of the molecules and the absence of chemomechanical activity. Furthermore, it was found that two polymorph modifications of the heterospin complex [Cu(hfac)2(Ln‐Pr)2] can be obtained, and magnetic properties of [Cu(hfac)2(Ln‐Pr)2] strongly depend on the angle between the planes of the paramagnetic fragment O—N‐C=N→O and the imidazole ring in Ln‐Pr.

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Molecular Magnets Based on Nickel(II) Complexes with 3-Imidazoline Nitroxides and Alcohols

Cited by 29 publications

References 17 publications

Metal–Nitroxide Complexes: Synthesis and Magnetostructural Correlations

Metal–Nitroxide Complexes: Synthesis and Magnetostructural Correlations

Crystal structure of polynuclear pivalate Ni(II) complexes with butanediol

N‐Alkylimidazol‐5‐yl‐substituted Nitronyl Nitroxides and Their Mononuclear Cu(II) Complexes: Synthesis, Structure and Magnetic Properties

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