6533b831fe1ef96bd129971f

RESEARCH PRODUCT

A new 3-D polymeric spin transition compound: [tris(1,4-bis(tetrazol-1-yl)butane-N1,N 1′)iron(II)] bis(perchlorate)

Jaap G. HaasnootYann GarciaEpiphane CodjoviAnthony L. SpekFrançois VarretPetra J. Van KoningsbruggenJorge LinaresOlivier KahnHuub Kooijman

subject

education.field_of_studyInorganic chemistryCatenanePopulationSpin transitionButaneGeneral ChemistryCrystal structurechemistry.chemical_compoundPerchlorateCrystallographychemistrySpin crossoverMössbauer spectroscopyeducation

description

A series of novel polymeric compounds of formula [M(btzb)3][ClO4]2 (Mll = Fe, Ni or Cu) with btzb = 1,4-bis-(tetrazol-1-yl)butane have been prepared and their physical properties investigated. The btzb ligand has been prepared and its crystal structure determined, together with a tentative crystal structure of the 3-D compound [Fe(btzb)3][ClO4]2. The model of the latter shows two symmetry-related, interpenetrating Fe-btzb networks in which the iron(II) ions approach each other as close as 8.3 and 9.1 A. This supramolecular catenane undergoes a sharp thermal spin transition around 160 K with hysteresis (20 K) along with a pronounced thermochromic effect. The spin crossover behaviour has been followed by magnetic, DSC, optical spectroscopy and 57Fe Mossbauer spectroscopy measurements. Irradiation with green light at low temperature leads to population of the metastable high-spin state for the thermally active iron(ll) ions. The nature of the spin crossover behaviour has been discussed in detail.

https://doi.org/10.1039/b008073j