Photomagnetic effect in a cyanide-bridged mixed-valence {FeII2FeIII2} molecular square

Mondal, Abhishake; Li, Yanling; Herson, Patrick; Seuleiman, Mannan; Boillot, Marie‐Laure; Rivière, Éric; Julve, Miguel; Rechignat, Lionel; Bousseksou, Azzedine; Lescouëzec, Rodrigue

doi:10.1039/c2cc17835d

Cited by 86 publications

(105 citation statements)

References 25 publications

(6 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Calculations were simplified to a cyano-bridged molecular square3839 formulated as [Fe II 2 – CN – Fe III 2 ] with a Tp − ligand on the Fe II ion, a pyridine ligand, and H 2 O on the Fe III ion (Fig. 4, and Supplementary Tables 5–7).…”

Section: Discussionmentioning

confidence: 99%

A ferromagnetically coupled Fe42 cyanide-bridged nanocage

et al. 2015

View full text Add to dashboard Cite

Self-assembly of artificial nanoscale units into superstructures is a prevalent topic in science. In biomimicry, scientists attempt to develop artificial self-assembled nanoarchitectures. However, despite extensive efforts, the preparation of nanoarchitectures with superior physical properties remains a challenge. For example, one of the major topics in the field of molecular magnetism is the development of high-spin (HS) molecules. Here, we report a cyanide-bridged magnetic nanocage composed of 18 HS iron(III) ions and 24 low-spin iron(II) ions. The magnetic iron(III) centres are ferromagnetically coupled, yielding the highest ground-state spin number (S=45) of any molecule reported to date.

show abstract

Section: Discussionmentioning

confidence: 99%

A ferromagnetically coupled Fe42 cyanide-bridged nanocage

et al. 2015

View full text Add to dashboard Cite

show abstract

“…Taking advantage of such feature, we synthesized and studied [Fe( R bik) 2 (NC-) 2 ] SCO systems, where one of the R bik ligand is replaced by two cyanido metallo-ligand, abbreviated (NC-). For example, we investigated two tetranuclear rhombus {Fe 2 M 2 } (M = Fe, Mo) switchable complexes containing the {Fe II ( R bik) 2 (NC-) 2 } subunit (NC- represents cyanido metallo ligand: [Fe III (Tp)(CN) 3 ] − or [Mo V (CN) 8 ] 3− ) (Mondal et al, 2012, 2014). Both complexes show gradual thermally-induced spin transition on the Fe(II) centers and photomagnetic effect (LIESST) at low temperature.…”

Section: Introductionmentioning

confidence: 99%

Thermally-Induced Spin Crossover and LIESST Effect in the Neutral [FeII(Mebik)2(NCX)2] Complexes: Variable-Temperature Structural, Magnetic, and Optical Studies (X = S, Se; Mebik = bis(1-methylimidazol-2-yl)ketone)

Chamoreau

Said

et al. 2018

Front. Chem.

Self Cite

View full text Add to dashboard Cite

Two new iron(II) neutral complexes of bis(1-methylimidazol-2-yl)ketone (Mebik) with molecular formula [FeII(Mebik)2(NCS)2] (1) and [FeII(Mebik)2(NCSe)2] (2) have been synthesized and characterized by magnetic measurements, single-crystal X-ray diffraction, and solid state UV-vis spectroscopy. The temperature dependent magnetic susceptibility measurements of crystalline samples of both compound show the occurrence of a gradual spin transition centered at T1/2 = 260 K and 326 K, respectively. The crystal structures of both compounds were determined at different temperatures, below and above the transition, in order to detect the structural changes associated with the spin transition. The main structural modifications, when passing from the low-spin to the high-spin form, consist of an important lengthening of the Fe-N(Mebik) and Fe-N (C-S/Se) distances (by ca. 0.20 and 0.18 Å, respectively) and a noticeable variation of the N-Fe-N angles, leading to a more distorted [Fe-N6] octahedron. The spin-transition phenomenon also affects the optical properties, with significant decrease of the intensity of the Metal-to-Ligand charge transfer band upon increasing the temperature. Finally, both complexes exhibit a light-induced excited spin-state trapping under laser light irradiation at low temperature. DFT calculations were also carried out on these complexes in order to rationalize the theoretically predicted magnetic and optical behavior with those of the experimental one. The results clearly highlights the dramatic alteration of the magneto-structural behavior of the tris-chelate [FeIIfalse(Mebik)3]2+ spin-crossover complex upon substituting one Mebik with NCS and NCSe ligands.

show abstract

“…SCO complexes show reversible transformation between a high-spin (HS) and a low-spin (LS) state [1][2][3][4][5][6][7] . In particular, the light-induced excited spin-state trapping (LIESST) [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] , which induces conversion of a LS state to a HS state by means of light irradiation, has attracted considerable interest. LIESST effects have been observed in various Fe II (or a few Fe III ) mononuclear complexes [19][20][21][22][23][24] .…”

mentioning

confidence: 99%

“…LIESST effects have been observed in various Fe II (or a few Fe III ) mononuclear complexes [19][20][21][22][23][24] . Moreover, SCO units and other paramagnetic ions have been linked via a short bridge to control intramolecular magnetic interactions [25][26][27][28][29][30][31][32][33] and generate magnetic ordering 34 via LIESST. However, no one has so far succeeded in introducing light-responsive SCO units into molecular nanomagnets, such as single-chain magnets (SCMs) and singlemolecule magnets, to switch the bistable states of the nanomagnets.…”

mentioning

confidence: 99%

“…Hence, the most effective approach towards tuning the SCM behaviour is to control directly the anisotropy of ions and intrachain magnetic interactions using external stimuli. LIESST can involve concomitant changes of spin state and anisotropy at the metal centres and subsequent changes of magnetic interaction pathways in the framework [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] . If the light-responsive SCO units can be incorporated in a chain, both the anisotropy of metal ions and the intrachain magnetic interactions will be tuned accompanying the LIESST effect [25][26][27][28][29][30][31][32][33][34] , producing a potential lightresponsive SCM.…”

mentioning

confidence: 99%

See 1 more Smart Citation

A light-induced spin crossover actuated single-chain magnet

et al. 2013

View full text Add to dashboard Cite

Both spin-crossover complexes and molecular nanomagnets display bistable magnetic states, potentially behaving as elementary binary units for information storage. It is a challenge to introduce spin-crossover units into molecular nanomagnets to switch the bistable state of the nanomagnets through external stimuli-tuned spin crossover. Here we report an iron(II) spincrossover unit and paramagnetic iron(III) ions that are incorporated into a well-isolated double-zigzag chain. The chain exhibits thermally induced reversible spin-crossover and lightinduced excited spin-state trapping at the iron(II) sites. Single-chain magnet behaviour is actuated accompanying the synergy between light-induced excited spin-state trapping at the iron(II) sites and ferromagnetic interactions between the photoinduced high-spin iron(II) and low-spin iron(III) ions in the chain. The result provides a strategy to switch the bistable state of molecular nanomagnets using external stimuli such as light and heat, with the potential to erase and write information at a molecular level.

show abstract

Photomagnetic effect in a cyanide-bridged mixed-valence {FeII2FeIII2} molecular square

Cited by 86 publications

References 25 publications

A ferromagnetically coupled Fe42 cyanide-bridged nanocage

A ferromagnetically coupled Fe42 cyanide-bridged nanocage

Thermally-Induced Spin Crossover and LIESST Effect in the Neutral [FeII(Mebik)2(NCX)2] Complexes: Variable-Temperature Structural, Magnetic, and Optical Studies (X = S, Se; Mebik = bis(1-methylimidazol-2-yl)ketone)

A light-induced spin crossover actuated single-chain magnet

Contact Info

Product

Resources

About