Iron(II) Mononuclear Materials Containing Functionalised Dipyridylamino-Substituted Triazine Ligands: Structure, Magnetism and Spin Crossover

2012 ◽  
Vol 65 (7) ◽  
pp. 874 ◽  
Author(s):  
Hayley S. Scott ◽  
Tamsyn M. Ross ◽  
Stuart R. Batten ◽  
Ian A. Gass ◽  
Boujemaa Moubaraki ◽  
...  

The spin crossover effect in iron(II) materials containing the di-2-pyridylamine functional group has been investigated for the new nitrile-functionalised ligand DTAC (2,2′,2″,2″′-((6-(di(pyridin-2-yl)amino)-1,3,5-triazine-2,4 diyl)bis(azanetriyl))tetra acetonitrile). This ligand has successfully been incorporated into a family of materials of the general formula trans-[Fe(DTAC)2(anion)2], wherein we have systematically varied the trans-nitrogen donor anion from NCS, NCSe, N(CN)2 (dca; dicyanamide) to NCBH3 – thus forming the four mononuclear materials trans-[Fe(DTAC)2(NCS)2]·6MeCN (1), trans-[Fe(DTAC)2(NCSe)2]·6MeCN (2), trans-[Fe(DTAC)2(N(CN)2)2] (3) and trans-[Fe(DTAC)2 (NCBH3)2]·3MeCN (4)). We find that the materials with a weaker crystal field strength anion remain high spin over all temperatures (1 and 2) whereas the materials containing stronger crystal field strength anions undergo a thermally induced spin crossover (3 and 4). Structural analysis revealed that the packing interactions in the solid state and the degree of solvation also play a large role in the observed magnetic behaviour. Indeed, aged or rapidly precipitated samples of 2 show a spin transition above room temperature.

1991 ◽  
Vol 44 (8) ◽  
pp. 1041 ◽  
Author(s):  
AT Baker ◽  
P Singh ◽  
V Vignevich

2,6-Di(thiazol-2-yl]pyridine (1a), 2,6-di(4-methylthiazol-2-yl)pyridine (1b) and 2,6-di(2-imid-azolin-2-yl)pyridine (3) have been prepared by the reaction of pyridine-2,6-dicarbothioamide with bromoacetaldehyde diethyl acetal, bromoacetone and ethylenediamine, severally. Bis ( ligand ) iron(II) and nickel(II) complexes of all ligands have been prepared. The bis ( ligand ) iron(II) complexes of (1a) and (3) are low-spin whereas that of (1b) is high-spin at room temperature and undergoes a thermally induced spin transition. The field strengths of the ligands , determined from the spectra of their nickel(II) complexes, correlate well with the observed magnetic behaviour of their iron(II) complexes. The field strengths of (1a) and (1b) are found to be marginally less than those of the isomeric ligands 2,6-di(thiazol-4-yl)pyridine (2a) and 2,6-di(2-methylthiazol-4-yl)pyridine (2b).


Author(s):  
Pradip Chakraborty ◽  
Mouhamadou Sy ◽  
Houcem Fourati ◽  
Maria Teresa Delgado Pérez ◽  
Mousumi Dutta ◽  
...  

The thermal spin transition and the photo-induced high-spin → low-spin relaxation of the prototypical [Fe(ptz)6](BF4)2 spin-crossover compound (ptz = 1-propyltetrazole) diluted in the isostructural ruthenium host lattice [Ru(ptz)6](BF4)2, which stabilizes...


Mineralogia ◽  
2009 ◽  
Vol 40 (1-4) ◽  
pp. 85-94 ◽  
Author(s):  
Sabina Bodył

Luminescence properties of Ce3+ and Eu2+ in fluorites and apatitesNatural samples of fluorite and apatite from granites, pegmatites, carbonatites and andesitic tuffs were investigated by steady-time spectroscopy to characterize the luminescence properties of Ce3+ and Eu2+. The luminescence of Ce3+ has been clearly seen in fluorite as 320 and 337 or 343 nm bands. In apatites, two distinct bands for two different Ca crystal sites were obtained: 340-380 nm for Ca(1) and 420-450 nm for Ca(2). The luminescence spectra of Eu2+ in the fluorite crystals were measured even at for low concentration of this element (0.11 ppm). For Ce3+, it has been showed that the crystal field strength depends more on the nature of the ligand than on the Me-ligand distances.


2013 ◽  
Vol 9 ◽  
pp. 342-391 ◽  
Author(s):  
Philipp Gütlich ◽  
Ana B Gaspar ◽  
Yann Garcia

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.


1984 ◽  
Vol 37 (6) ◽  
pp. 1157 ◽  
Author(s):  
AT Baker ◽  
HA Goodwin

The tris[2-(pyridin-2-yl)benzothiazole]iron(II) ion has been isolated as the tetraphenylborate salt which is stable in the atmosphere for short periods. The deep red complex displays a temperature-dependent magnetic moment and thermochroism which are associated with a thermally induced singlet (1A1) ↔ quintet (5T2) spin transition. An empirical treatment of the transition, which is continuous, yields ∆H and ∆S values of 22.7 kJ mol-1 and 91 JK-1 mol-1 over the range 275-364 K. Spectral data for the corresponding nickel(11) complex confirm the intermediate nature of the field strength of the benzothiazole and indicate that it is a weaker ligand than the corresponding thiazole derivative.


2015 ◽  
Vol 54 (16) ◽  
pp. 7906-7914 ◽  
Author(s):  
Francisco Javier Valverde-Muñoz ◽  
Ana B. Gaspar ◽  
Sergii I. Shylin ◽  
Vadim Ksenofontov ◽  
José A. Real

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