A large series of Chromium(III) and Cobalt(II) complexes containing the C4O4 (squarate) ligand have been synthesized and characterized... Show moreA large series of Chromium(III) and Cobalt(II) complexes containing the C4O4 (squarate) ligand have been synthesized and characterized magnetically. These complexes include simple dimeric Cr(III) systems that display a wide range of isotropic exchange couplings. One of these dimers shows interesting biological activity pertaining to the cellular uptake of glucose. This same compound also enhanced proton relaxation in T1 and T2 NMR studies. Computational work done on these dimeric systems showed excellent agreement with experimental results, and was used to confirm the structure of the complexes. The effect of the bridging squarate ligand was also studied computationally. The squarate ligand significantly contributed to the exchange coupling in the dimeric systems, and was shown to behave countercomplementary to the μ-hydroxo bridges. This is the first explicit observation of countercomplementarity in Chromium(III) systems. Co3(OH)2(C4O4) · 3H2O, a cobalt chain structure featuring an interesting low temperature spin-idle phase, was also synthesized. It was found that based on storage conditions, this compound either stays stable after grinding or transforms into the structure Co(C4O4)(H2O)2. In addition, grinding the sample shows an out-of-phase maxima at ≥6 K that has a frequency dependence characteristic of a spin glass. A new software package was also developed to simulate Electron Paramagnetic Resonance (EPR) spectra using full numerical diagonalization of the secular equation. This program was written using Wolfram Mathematica, and holds several advantages over currently available software. These advantages include a graphical user-interface and parallelization capabilities PH.D in Chemistry, July 2013 Show less
