Slow magnetic relaxation in a complex of photochromic spiropyran in a merocyanine form and cobalt(II) hexafluoroacetylacetonate.

The interaction between photochromic 8-methoxy-1',3',3'-trimethyl-6-nitro-spiro[chromene-2,2'-indole] (MNSP) and cobalt(II) hexafluoroacetylacetonate yields a deep red-violet solution due to the coordination-induced transition of MNSP from a colorless closed state to a colored open merocyanine (MC) form. The resulting complex {Co(hfac)·MNSP} (1) is obtained as crystals, and its structure at 250 K shows the coordination of two oxygen atoms from MNSP with Co, forming a distorted octahedral surrounding around Co. The unit cell of 1 contracts below 170 K by 5.5%, which is accompanied by shortening O-Co bonds and altering O-Co-O angles in the structure solved at 150 K. The value of 3.06 emu K mol at 300 K indicates the formation of high-spin Co ( = 3/2) with a large orbital contribution characteristic of the octahedral surrounding. The contraction of the unit cell of 1 below 170 K provides a reversible 2.2% change of in the 170-160 K range during heating and cooling regimes without hysteresis. The electron paramagnetic resonance signal of 1 was simulated with -values of = 2.342, = 2.364, and = 2.084, and an isotropic -factor of 2.267. The temperature-dependent and field-dependent magnetization of 1 allow us to determine a positive zero-field splitting parameter of +20.1 cm. A study of the dynamic properties of 1 shows slow magnetic relaxation for Co in a static field of 1000 Oe. Magnetic hysteresis loops were observed for 1 at 0.5 and 2 K; these loops are closed in the zero field region but opened at fields higher than ±100 and 700 Oe, respectively. The collapse of the loop is observed at 5 K. Excitation of the solution of 1 with green light decreases partially the intensity of the bands of the complex, whereas subsequent exposure of this solution to UV light partially restores these intensities.