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Thermal and light-induced spin switching dynamics in the 2D coordination network of {[Zn1-xFex(bbtr)3](ClO4)2}∞: the role of cooperative effects.
Autorzy
Rok wydania
2012
Czasopismo
Numer woluminu
51
Strony
9714-9722
DOI
10.1021/ic301006c
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The thermal spin transition, the photoexcitation, and thesubsequent spin relaxation in the mixed crystal series of the covalentlylinked two-dimensional network {[Zn1‑xFex(bbtr)3](ClO4)2}∞(x= 0.02−1,bbtr =1,4-di(1,2,3-triazol-1-yl)-butane) are discussed. In the neat com-pound, the thermal spin transition with a hysteresis of 13 K is accompaniedby a crystallographic phase transition (Kusz, J.; Bronisz, R.; Zubko, M.;Bednarek, H.Chem. Eur. J.2011,17, 6807). In contrast, the diluted crystalswithx≤0.1 stay essentially in the high-spin state down to low temperaturesand show typicalfirst order relaxation kinetics upon photoexcitation, andthe structural phase transition is well separated from the spin transition.With increasing Fe(II) concentration, steeper thermal transitions andsigmoidal relaxation curves indicate increasingly important cooperativeeffects. Already atx= 0.38, the spin relaxation is governed by cooperativeinteractions between Fe(II) centers, and the crystallographic phasetransition begins to influence the spin transition. The kinetic behavior of the thermal spin transition is reproduced within theframework of a dynamic mean-field model
Adres publiczny
http://dx.doi.org/10.1021/ic301006c
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