Structure and energy stability of lanthanum and lutetium trihalide dimer molecules

Solomonik, V. G.; Смирнов, А. Н.

doi:10.1007/s10947-006-0230-y

Cited by 6 publications

(2 citation statements)

References 9 publications

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“…Such bridges are common in the solid state, where a ligand bridging two larger cations is also coordinated to a smaller one, as present in, for example, the crystalline lattices of La 2 CuO 4 or the K–Ag(II)–F series. Concurrently, the cluster geometry derives partly from the postulated Ln 2 F 6 molecules − and bridges present in some larger molecular magnets with Ln–(μ 2 -X) 2 –Ln bridges. − Here, − the AgF + group is added, in a perpendicular orientation, to the center of the Ln–X–Ln bridge with other fluorides mainly stabilizing the central part. The chosen molecular clusters proved their stability in numerous geometry optimization runs and as such serve as a test bed for the spin–spin interactions …”

Section: Resultsmentioning

confidence: 99%

Ag(II) as Spin Super-Polarizer in Molecular Spin Clusters

et al. 2022

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Using quantum mechanical calculations, we examine magnetic (super)exchange interactions in hypothetical, chemically reasonable molecular coordination clusters containing fluoride-bridged late transition metals or selected lanthanides, as well as Ag(II). By referencing to analogous species comprising closed-shell Cd(II), we provide theoretical evidence that the presence of Ag(II) may modify the magnetic properties of such systems (including metal−metal superexchange) to a surprising degree, specifically both coupling sign and strength may markedly change. Remarkably, this happens in spite of the fact that the fluoride ligand is the least susceptible to spin polarization among all monoatomic ligands known in chemistry. In an extreme case of an oxo-bridged Ni(II) 2 complex, the presence of Ag(II) leads to a nearly 17-fold increase of magnetic superexchange and switching from antiferro (AFM)-to ferromagnetic (FM) coupling. Ag(II)�with one hole in its d shell that may be shared with or transferred to ligands� effectively acts as spin super-polarizer, and this feature could be exploited in spintronics and diverse molecular devices.

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Section: Resultsmentioning

confidence: 99%

Ag(II) as Spin Super-Polarizer in Molecular Spin Clusters

et al. 2022

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“…The other reason is that the lanthanide ions have to be applied in 3-4 orders of magnitude excess (10 -3 -10 -2 M), compared to the porphyrin concentration, to push the equlibrium towards the complex formation. In such a concentration, lanthanide(II I) ions compose oligomers through the counter-anion or hydroxide bridges in aqueous solution [36,37]. Therefore, the pre-dissociation of these oligomers is required for the formation of porphyrin complexes because only the monomer lanthanide ion is able to insert into the coordination cavity.…”

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Peculiarities of the reactions between early lanthanide(III) ions and an anionic porphyrin

Kiss

Imran

Szentgyörgyi

et al. 2014

Inorganic Chemistry Communications

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Insertion of early lanthanide(III) ions into the coordination cavity of porphyrins is a slow and complicated process in aqueous solution, originating from the stability of their aqua complexes and their possible oligomerization. The presence of potential axial ligands can accelerate the coordination of the first porphyrin, but it can hinder the connection of a further porphyrin. Lanthanide ions may coordinate not only to the pyrrolic nitrogens of porphyrins but, under kinetic control, also to the peripheral substituents possessing O-donor atoms. In the case of such anionic porphyrins, the coordination position of metal ions can be influenced by the change of temperature. Keywords: simultaneous metal and ligand control, out-of-plane metalloporphyrins, early lanthanide(III) ions, axial enhancement or hindrance, tail-to-tail oligomerization.

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