Photomagnetism of a Series of Dinuclear Iron(II) Complexes



Spin crossover: The photomagnetic properties of a series of [{Fe(NCS)(py-X)}2(bpypz)2] (NCS=thiocyanate, py=pyridine, X=4-Mepy, py, 3-Mepy, 3-Clpy and 3-Brpy, and bpypz=3,5-bis(pyridine-2-yl)pyazolate) binuclear complexes are close to the antiferromagnetic response of [{Fe(NCS)(3,5-dmpy)}3(bpypz)2] (3,5-dmpy=3,5-dimethylpyrazine), which is characterised by two iron(II) metal ions in a high-spin (HS) electronic configuration (see figure).

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This paper describes the photomagnetic properties of a series of binuclear iron(II) complexes belonging to the [{Fe(NCS)(py-X)}2(bpypz)2] family (NCS=thiocyanate; py=pyridine; bpypz=3,5-bis(pyridine-2-yl)pyrazolate; and py-X=4-Mepy (1), py (3), 3-Mepy (4), 3-Clpy (5), and 3-Brpy (6)). All of these complexes display a complete thermal spin transition centred between 100 and 150 K, and undergo the light-induced excited-spin-state trapping (LIESST) effect at low temperatures. The T(LIESST) relaxation temperature of the photoinduced high-spin state for each compound has been determined. For all of the complexes, it has been found that the T(LIESST) curves at low temperature are close to the antiferromagnetic response of the [{Fe(NCS)(3,5-dmpy)}2(bpypz)2] (3,5-dmpy=3,5-dimethylpyridine) (7) complex that is characterised by two iron(II) metal ions in a HS electronic configuration, giving some evidence of a quantitative low spin–low spin→high spin–high spin (LS–LS→HS–HS) photoconversion process. Depending on the nature of the cooperativity, the kinetics have been treated with stretched exponential, simply exponential, or sigmoidal models. Interestingly, this series of dinuclear complexes follows a previously proposed linear relationship between the T(LIESST) and their thermal spin transition temperatures T1/2: T(LIESST)=T0−0.3T1/2. T0 for these compounds is equal to 100 K. Based on this, and by using the empirical linear relationship found between the thermal spin transition and the Hammett constant, the HS–HS properties of complex 7 have been understood as a reflection of the physical impossibility that the T(LIESST) was higher than T1/2. The close vicinity of the thermal spin-crossover phenomenon of 7 has been successfully checked by applying hydrostatic pressure.