First Iron(II) Spin-crossover Complex with an N5S Coordination Sphere

Yamasaki, Masaru; Ishida, Takayuki

doi:10.1246/cl.150301

Cited by 21 publications

(32 citation statements)

References 19 publications

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“…106 In the third case, NCS anions doubly bridge the Fe(II) centres with N 5 S coordination environments and L37 capping ligands (Chart 8). 107 The fourth example features a diiminoquinonoid-bridges (A2-A5, Chart 7) with L35 capping ligands (Chart 8). 108 Real and co-workers reported the first example, a dicyanamide bridged Fe(II) SCO-active dinuclear complex, in 2005, 105 [Fe 2 L34 2 (dca)](PF 6 ) 3 ÁnH 2 O (n = 1 and 0).…”

Section: Assorted Anion Bridged Dinuclear Complexesmentioning

confidence: 99%

Spin crossover in discrete polynuclear iron(ii) complexes

2018

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Iron(ii) spin crossover (SCO) materials have been widely studied as molecular switches with a wide variety of potential applications, including as displays, sensors, actuators or memory components. Most SCO materials have been either monometallic or polymeric, and it is only relatively recently that chemists have really started to focus on linking multiple metal centres together within the one, discrete, molecule in an effort to enhance the SCO properties, such as abrupt, hysteretic, and multistep switching, as well as the potential for quantum cellular automata, whilst still being readily amenable to characterisation. Here we present a review of the ligand designs of the last two decades that have led to self assembly of discrete di- to poly-nuclear iron(ii) complexes of helicate, cage, cube, and other supramolecular architectures with rich SCO activity, and to an increased focus on host-guest interactions. Analysis of selected octahedral distortion parameters (Σ, CShM) reveals interesting differences between these structural types, for example that the iron(ii) centres in grids are generally significantly more distorted than those in squares or cages, yet are still SCO-active. Of the 127 complexes reviewed (79 published 2012-Feb. 2018), 54% are dinuclear, 10% trinuclear, 31% tetranuclear, and the remaining 5% are penta, hexa and octanuclear. Of the 93 designer ligands utilised in these polynuclear architectures: 60 feature azoles; 55 provide all donors to the Fe(ii) centres (no co-ligands coordinated) and form exclusively 5-membered chelate rings via either bidentate azole-imine/pyridine or tridentate heterocycle-imine/amine/thioether/pyridine-heterocycle binding pockets.

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Section: Assorted Anion Bridged Dinuclear Complexesmentioning

confidence: 99%

Spin crossover in discrete polynuclear iron(ii) complexes

2018

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“…Multinuclear SCO complexes have been investigated intensively within the last 15 years, exhibiting promising SCO behaviours for possible applications, in particular binuclear complexes. [57][58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76] Compared to spin state switching in mononuclear compounds, multinuclear complexes promise more drastic changes of the macroscopic material properties. For instance, the total amount of unpaired electrons -and therefore the magnetic moment -as well as their coupling could accumulate over all metallic centres, increasing interactions compared to those in mononuclear complexes (e.g.…”

Section: 56mentioning

confidence: 99%

Spin state switching of metal complexes by visible light or hard X-rays

et al. 2016

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Electromagnetic stimuli of spin crossover compounds restricted to UV-vis light irradiation for many years could be recently extended to X-ray excitation. This review covers a large variety of light-induced effects, as well as recent analogues stimulated by X-ray irradiation which have not yet been reviewed. The focus is also on multistable multinuclear spin crossover compounds which are the subject of lively discussions within the spin crossover community. Their spin transition often occurs incompletely and with different switching mechanisms. In this review, we recall a predicted sequential switching induced thermally as well as a concerted stimulation mechanism by light irradiation for these interesting multifunctional materials.

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“…Notably, all these complexes feature the Fe II N 6 chromophore that is frequently considered as a prerequisite for the existence of the SCO. However, a handful of SCO complexes with Fe II N 4 O 2 , 12 Fe II N 5 O, 13 Fe II N 4 S 2 , 14 Fe II N 5 S, 15 Fe II N 4 C 2 , 16 Fe II N 3 C 2 O 2 17 and even FeC 3 N 18 coordination spheres have been also reported. Ferrous complexes bearing at least one chloride ligand exist in the HS state due to the relatively large anionic radius of the chloride anion and its associated weak ligand field strength.…”

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confidence: 99%