Soft-x-ray-induced spin-state switching of an adsorbed Fe(II) spin-crossover complex

A series of three different solvatomorphs of a new iron(II) complex with N,N′-disubstituted 2,6-bis(pyrazol-3-yl)pyridine, including those with the same lattice solvent, has been identified by X-ray diffraction under the same crystallization conditions with the metal ion trapped in the different spin states. A thermally induced switching between them, however, occurs in a solution, as unambiguously confirmed by the Evans technique and an analysis of paramagnetic chemical shifts, both based on variable-temperature NMR spectroscopy. The observed stabilization of the high-spin state by an electron-donating substituent contributes to the controversial results for the iron(II) complexes of 2,6-bis(pyrazol-3-yl)pyridines, preventing ‘molecular’ design of their spin-crossover activity; the synthesized complex being only the fourth of the spin-crossover (SCO)-active kind with an N,N′-disubstituted ligand.

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Spin state switching in iron coordination compounds

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.9.39 ◽

2013 ◽

Vol 9 ◽

pp. 342-391 ◽

Cited By ~ 446

Author(s):

Philipp Gütlich ◽

Ana B Gaspar ◽

Yann Garcia

Keyword(s):

Spin State ◽

Coordination Compounds ◽

Spin Crossover ◽

Spin Transition ◽

Pressure Sensors ◽

Ligand Field ◽

Thermally Induced ◽

Practical Applications ◽

State Switching ◽

Switching Phenomenon

The article deals with coordination compounds of iron(II) that may exhibit thermally induced spin transition, known as spin crossover, depending on the nature of the coordinating ligand sphere. Spin transition in such compounds also occurs under pressure and irradiation with light. The spin states involved have different magnetic and optical properties suitable for their detection and characterization. Spin crossover compounds, though known for more than eight decades, have become most attractive in recent years and are extensively studied by chemists and physicists. The switching properties make such materials potential candidates for practical applications in thermal and pressure sensors as well as optical devices. The article begins with a brief description of the principle of molecular spin state switching using simple concepts of ligand field theory. Conditions to be fulfilled in order to observe spin crossover will be explained and general remarks regarding the chemical nature that is important for the occurrence of spin crossover will be made. A subsequent section describes the molecular consequences of spin crossover and the variety of physical techniques usually applied for their characterization. The effects of light irradiation (LIESST) and application of pressure are subjects of two separate sections. The major part of this account concentrates on selected spin crossover compounds of iron(II), with particular emphasis on the chemical and physical influences on the spin crossover behavior. The vast variety of compounds exhibiting this fascinating switching phenomenon encompasses mono-, oligo- and polynuclear iron(II) complexes and cages, polymeric 1D, 2D and 3D systems, nanomaterials, and polyfunctional materials that combine spin crossover with another physical or chemical property.

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Unidirectional electric field-induced spin-state switching in spin crossover based microelectronic devices

Chemical Physics Letters ◽

10.1016/j.cplett.2015.11.036 ◽

2016 ◽

Vol 644 ◽

pp. 138-141 ◽

Cited By ~ 28

Author(s):

Constantin Lefter ◽

Reasmey Tan ◽

Julien Dugay ◽

Simon Tricard ◽

Gábor Molnár ◽

...

Keyword(s):

Electric Field ◽

Spin State ◽

Spin Crossover ◽

Microelectronic Devices ◽

State Switching

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Linking Electronic Transport through a Spin Crossover Thin Film to the Molecular Spin State Using X-ray Absorption Spectroscopy Operando Techniques

ACS Applied Materials & Interfaces ◽

10.1021/acsami.8b11495 ◽

2018 ◽

Vol 10 (37) ◽

pp. 31580-31585 ◽

Cited By ~ 13

Author(s):

Filip Schleicher ◽

Michał Studniarek ◽

Kuppusamy Senthil Kumar ◽

Etienne Urbain ◽

Kostantine Katcko ◽

...

Keyword(s):

Thin Film ◽

Absorption Spectroscopy ◽

Spin State ◽

Electronic Transport ◽

Spin Crossover ◽

X Ray ◽

Molecular Spin ◽

X Ray Absorption

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Spin Crossover Metal-Organic Frameworks with Inserted Photoactive Guests: On the Quest to Control the Spin State by Photoisomerization

Dalton Transactions ◽

10.1039/d1dt01057c ◽

2021 ◽

Author(s):

Barbora Brachnakova ◽

Jan Moncol ◽

Jan Pavlik ◽

Ivan Salitros ◽

Sébastien Bonhommeau ◽

...

Keyword(s):

Spin State ◽

Elemental Analysis ◽

Spin Crossover ◽

Metal Organic Frameworks ◽

X Ray Diffraction ◽

Guest Molecules ◽

X Ray ◽

Trans Stilbene ◽

Metal Organic ◽

Trans Azobenzene

Three Hofmann-like metal-organic frameworks {Fe(bpac)[Pt(CN)4]}·G (bpac=1,2-bis(4-pyridyl)acetylene) were synthesized with photoisomerizable guest molecules (G = trans-azobenzene, trans-stilbene or cis-stilbene) and were characterized by elemental analysis, thermogravimetry and powder X-ray diffraction. The...

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Fe(Me2-bpy)2(NCSe)2spin-crossover micro- and nanoparticles showing spin-state switching above 250 K

New Journal of Chemistry ◽

10.1039/c4nj01257g ◽

2015 ◽

Vol 39 (3) ◽

pp. 1603-1610 ◽

Cited By ~ 9

Author(s):

Luong Lam Nguyen ◽

Régis Guillot ◽

Jérôme Laisney ◽

Lionel Rechignat ◽

Salma Bedoui ◽

...

Keyword(s):

Solid State ◽

Spin State ◽

Spin Crossover ◽

State Switching

Nano- and microparticles or polycrystalline powders of the Fe(Me2-bpy)2(NCSe)2spin-crossover complex were easily elaborated from the diamagnetic precursor [Fe(Me2-bpy)3](NCSe)2·S by precipitation in an anti-solvent or by solid-state thermolysis.

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Anomalous Light‐Induced Spin‐State Switching for Iron(II) Spin‐Crossover Molecules in Direct Contact with Metal Surfaces

Angewandte Chemie International Edition ◽

10.1002/anie.202003896 ◽

2020 ◽

Vol 59 (32) ◽

pp. 13341-13346 ◽

Cited By ~ 2

Author(s):

Luqiong Zhang ◽

Yongfeng Tong ◽

Massine Kelai ◽

Amandine Bellec ◽

Jérôme Lagoute ◽

...

Keyword(s):

Spin State ◽

Direct Contact ◽

Metal Surfaces ◽

Spin Crossover ◽

State Switching

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A homochiral 3D framework of mechanically interlocked 1D loops with solvent-dependent spin-state switching behaviors

Chemical Communications ◽

10.1039/c9cc09063k ◽

2020 ◽

Vol 56 (1) ◽

pp. 133-136

Author(s):

Xiao-Peng Sun ◽

Zheng Tang ◽

Zi-Shuo Yao ◽

Jun Tao

Keyword(s):

Single Crystal ◽

Spin State ◽

Spin Crossover ◽

Crystal Transformation ◽

State Switching ◽

One Step ◽

3D Framework

A homochiral 3D mechanically interlocked framework based on 1D loops is presented, which shows reversible single-crystal-to-single-crystal transformation and enables the interconversion between one-step and two-step spin crossover behaviors.

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Spin State Transition Studied by Means of Optical Microscope

Solid State Phenomena ◽

10.4028/www.scientific.net/ssp.163.46 ◽

2010 ◽

Vol 163 ◽

pp. 46-50 ◽

Cited By ~ 1

Author(s):

Maciej Zubko ◽

Paweł Zajdel ◽

Joachim Kusz

Keyword(s):

Spin State ◽

Spin Crossover ◽

State Transition ◽

Optical Microscope ◽

X Ray ◽

Spin State Transition ◽

Transmission Geometry ◽

One Step ◽

Analysis Of Change

We have tested a new method which allows assigning the spin state of the spin crossover (SCO) crystal in-situ during the diffraction experiment. The method is based on the analysis of change of the colour of the SCO compounds. We have found that the off-line setup in transmission geometry is reliable in assigning the magnitude of high spin molecules fraction (γHS) and the character (one step, many steps, histeresis) of the SCO transition. Later on, this method has been used in the in-situ measurements directly on X-ray four-circle diffractometer.

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