New Spin-Transition-Like Copper(II)−Nitroxide Species

Hirel, Catherine; Li, Licun; Brough, Peter; Vostrikova, Kira E.; Pécaut, Jacques; Mehdaoui, B.; Bernard, Maxime; Turek, Philippe; Rey, P.

doi:10.1021/ic700851x

Cited by 36 publications

(19 citation statements)

References 35 publications

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“…In a Cu II -nitroxide cluster, [Cu(hfac) 2 ] 4 L 2 , (hfac = hexafluoroacetylacetonato, L = 2-(3-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydrlo-1H-imidazolyl-1-oxy-3-oxide), a thermally induced switch between HS (six S = 1/2 spins) and LS (two S = 1/2 spins) was observed 118 . The spin-transition-like behaviour arises from the change in the magnetic interaction between Cu II and the nitroxide radical, which is derived from an equatorial-axial conversion of coordination of an oxyl oxygen in the Cu II -nitroxide cluster 119 . Recently, 1D Cu II -nitroxide compounds have also been found to exhibit a LIESST-like effect 120,121 .…”

Section: Change In Molecular Structurementioning

confidence: 99%

Dynamic molecular crystals with switchable physical properties

2016

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The development of molecular materials whose physical properties can be controlled by external stimuli - such as light, electric field, temperature, and pressure - has recently attracted much attention owing to their potential applications in molecular devices. There are a number of ways to alter the physical properties of crystalline materials. These include the modulation of the spin and redox states of the crystal's components, or the incorporation within the crystalline lattice of tunable molecules that exhibit stimuli-induced changes in their molecular structure. A switching behaviour can also be induced by changing the molecular orientation of the crystal's components, even in cases where the overall molecular structure is not affected. Controlling intermolecular interactions within a molecular material is also an effective tool to modulate its physical properties. This Review discusses recent advances in the development of such stimuli-responsive, switchable crystalline compounds - referred to here as dynamic molecular crystals - and suggests how different approaches can serve to prepare functional materials.

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Section: Change In Molecular Structurementioning

confidence: 99%

Dynamic molecular crystals with switchable physical properties

2016

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“…210 To summarize the discussion of these surprising heterospin complexes, it should be emphasized that their detection is one of achievements in the field of molecular magnetism. 218 …”

Section: Breathing Crystalsmentioning

confidence: 99%

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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“…They are good candidates not only for fundamental studies of magnetic-structural correlations, especially how the structural factors affect the interaction between metal and radical, but also for the development of novel molecular magnetic materials. One method for obtaining such cyclic complexes is to use nitroxides substituted by a nitrogen-containing group, which can not function as a chelating ligand such as 3-pyridyl [27] and phenylpyrimidyl groups [28]. Along this line, we use 2-[(4-carboxyl)phenyl]-4,4,5,5-tetramethylimidazoline-1-oxy-3-oxide (NITPBAH) with non-chelating carboxyl group to build new cyclic metal-radical complexes.…”

Section: Introductionmentioning

confidence: 99%