Spin crossover iron(III) complexes

Nihei, Masayuki; Shiga, Tohru; Maeda, Yonezo; Oshio, Hiroki

doi:10.1016/j.ccr.2007.08.007

Cited by 272 publications

(188 citation statements)

References 115 publications

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“…Expanded chelate ring sizes should also promote the high spin states of complexes, by increasing the ligand conformational strain associated with the more compact low-spin form [71,72] [75,76], for example, although that remains to be confirmed by a solution-phase study. It is harder to elucidate trends from those compounds in the solid state, since their SCO is often very gradual and can be influenced by the salicyl ligand conformation in the crystal [68].…”

Section: Influence Of Chelate and Macrocycle Ring Size On Metal Ion Smentioning

confidence: 99%

The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes

2016

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Abstract:The relationship between chemical structure and spin state in a transition metal complex has an important bearing on mechanistic bioinorganic chemistry, catalysis by base metals, and the design of spin crossover materials. The latter provide an ideal testbed for this question, since small changes in spin state energetics can be easily detected from shifts in the spin crossover equilibrium temperature. Published structure-function relationships relating ligand design and spin state from the spin crossover literature give varied results. A sterically crowded ligand sphere favors the expanded metal-ligand bonds associated with the high-spin state. However, steric clashes at the molecular periphery can stabilize either the high-spin or the low-spin state in a predictable way, depending on their effect on ligand conformation. In the absence of steric influences, the picture is less clear since electron-withdrawing ligand substituents are reported to favor the low-spin or the high-spin state in different series of compounds. A recent study has shed light on this conundrum, showing that the electronic influence of a substituent on a coordinated metal ion depends on its position on the ligand framework. Finally, hydrogen bonding to complexes containing peripheral N-H groups consistently stabilizes the low-spin state, where this has been quantified.

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Section: Influence Of Chelate and Macrocycle Ring Size On Metal Ion Smentioning

confidence: 99%

The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes

2016

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“…We point out that these values are characteristic for low-spin complexes with Fe(II) or Fe(III) [17,18].…”

Section: Resultsmentioning

confidence: 74%

Exchange Interaction in Complex Bis[(1,3-Dithiole-2-Thione-4,5-Dithiolato)-di-(Carbonyl)-Cyclopentadienyl Iron(II)]

Vitushkina

Ziolkovskiy

Стародуб

et al. 2009

Research Letters in Inorganic Chemistry

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The splitting of the quasidegenerate electronic states in dinuclear bis[(1,3-dithiole-2-thione-4,5-dithiolato)-di-(carbonyl)-cyclopentadienyliron (II)] complex with the bridging, S-S coupled, dimerized sulfur-rich dithiolate ligands, [Fe(C 5 H 5 )(CO) 2 (C 3 S 5 -C 3 S 5 )Fe(C 5 H 5 )(CO) 2 ] (I) was found by the means of Mössbauer spectroscopy and by the measurement of the temperature dependence of magnetic susceptibility in a wide temperature range from 2 K to 300 K. The experimental results were confirmed by the calculations of the singlet and triplet states of the complex, as well as of the distribution of spin density within the bounds of the DFT method in the B3LYP/6-31(dp)G basis. In the more stable triplet state, the spin density is significantly delocalized, which is a characteristic of olefindithiolate complexes.

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“…The first member of the now prototypical Fe(II)N 6 family was described thirty years later with the discovery of SCO in Fe(phen) 2 (NCS) 2 [40][41][42][43], one of the most studied SCO complexes [44][45][46][47][48][49]. Ever since, a huge amount of hexacoordinated Fe(II) and Fe(III) complexes has been synthesized and their magnetic properties have extensively been studied [2,4,[50][51][52][53] . More recently, attention is shifting towards other metals and coordination modes [54].…”

Section: Thermal Scomentioning

confidence: 99%

“…The most widely studied complexes are based on the prototypical Fe(II)N 6 core, but other ions and coordination spheres are becoming more and more important in the field [2,4,191]. In fact, the first description of SCO concerned an Fe(III) complex [39], and nowadays many more Fe(III) complexes have been reported [53,192]. The so-called lightinduced excited spin state trapping (LIESST), which triggers the spin transformation from a low spin state (LS) to a metastable high spin state (HS) by light, has received special attention both in experimental and computational studies because it o↵ers an optimal control on the SCO process.…”

Section: Introductionmentioning

confidence: 99%

From Mononuclear to Dinuclear: Magnetic Properties of Transition Metal Complexes

Saureu¹

2016

ioChem-BD Computational Chemistry Datasets

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Spin crossover iron(III) complexes

Cited by 272 publications

References 115 publications

The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes

The Effect of Ligand Design on Metal Ion Spin State—Lessons from Spin Crossover Complexes

Exchange Interaction in Complex Bis[(1,3-Dithiole-2-Thione-4,5-Dithiolato)-di-(Carbonyl)-Cyclopentadienyl Iron(II)]

From Mononuclear to Dinuclear: Magnetic Properties of Transition Metal Complexes

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