7519-90-6Relevant articles and documents
Polymorphism in Fe[(p-IC6H4)B(3-Mepz) 3]2 (pz = Pyrazolyl): Impact of supramolecular structure on an Iron(ll) electronic Spin-state crossover
Reger, Daniel L.,Gardinier, James R.,Smith, Mark D.,Shahin, Ahmed M.,Long, Gary J.,Rebbouh, Leila,Grandjean, Fernande
, p. 1852 - 1866 (2005)
The new ligands Na[(p-IC6H4)B(3-Rpz)3] (R = H, Me) have been prepared by converting I2C6H 4 to IC6H4SiMe3 with Li +Bu and SiMe3Cl, and then to IC6H 4BBr2 with BBr3 and subsequent reaction with 3 equiv of (un)substituted pyrazole and 1 equiv of NaO+Bu. These new ligands react with FeBr2 to give either purple, low-spin Fe[(p-IC6H4)B(pz)3]2 or colorless, high-spin Fe[(p-IC6H4)B(3-Mepz)3]2. Depending upon the crystallization conditions, Fe[(p-IC6H 4)B(3-Mepz)3]2 can exist both as two polymorphs and as a methylene chloride solvate. An examination of these polymorphs by variable-temperature X-ray crystallography, magnetic susceptibility, and Moessbauer spectroscopy has revealed different electronic spin-state crossover properties for each polymorph and yields insight into the influence of crystal packing, independent of other electronic perturbations, on the spin-state crossover. The first polymorph of Fe[(p-IC6H 4)B(3-Mepz)3]2 has a highly organized three-dimensional supramolecular structure and does not undergo a spin-state crossover upon cooling to 4 K. The second polymorph of Fe[(p-IC 6H4)B(3-Mepz)3]2 has a stacked two-dimensional supramolecular structure, a structure that is clearly less well organized than that of the first polymorph, and undergoes an abrupt iron(II) spin-state crossover from high spin to low spin upon cooling below ca. 130 K. The crystal structure of the methylene chloride solvate of Fe[(p-IC 6H4)B(3-Mepz)3]2 has a similar stacked two-dimensional supramolecular structure, but the crystals readily lose the solvate. The resulting desolvate undergoes a gradual spin-state crossover to the low-spin state upon cooling below ca. 235 K. It is clear from a comparison of the structures that the longrange solid-state organization of the molecules, which is controlled by noncovalent supramolecular interactions, has a strong impact upon the spin-state crossover, with the more highly organized structures having lower spincrossover temperatures and more abrupt spin-crossover behavior.
