Lawrence Berkeley National Laboratory

The addition of various dipolar molecules is shown to affect the temperature dependence of the spin state occupancy of the much studied spin crossover Fe(II) complex, [Fe{H₂B(pz)₂}₂(bipy)] (pz  =  pyrazol-1-yl, bipy  =  2,2'-bipyridine). Specifically, the addition of benzimidazole results in a re-entrant spin crossover transition, i.e. the spin state starts in the mostly low spin state, then high spin state occupancy increases, and finally the high spin state occupancy decreases with increasing temperature. This behavior contrasts with that observed when the highly polar p -benzoquinonemonoimine zwitterion C₆H₂(…NH₂)₂(…O)₂ was mixed with [Fe{H₂B(pz)₂}₂(bipy)], which resulted in locking [Fe{H₂B(pz)₂}₂(bipy)] largely into a low spin state while addition of the ethyl derivative C₆H₂(…NHC₂H₅)₂(…O)₂ did not appear to perturb the spin crossover transition of [Fe{H₂B(pz)₂}₂(bipy)].