| The preparation and characterization of metallo-beta-oxochlorin and the pi-cation radical derivatives of metallo-beta-oxochlorins is described. The pi-cation radical derivatives are prepared by the oxidation of neutral metallo-beta-oxochlorin complexes ([M(oxoOEC)], M = Cu(II) and Fe(III)) with one-electron oxidants yielding complexes with the formula [M(oxoOEC ·)]SbCl6 (oxoOEC = (3,3,7,8,12,13,17,18-octaethyl-(3 H)-porphin-2-onato) dianion). The characterization of these species both before and after the one-electron oxidations allows for a complete analysis of the effects of macrocyclic ring oxidation. A thorough investigation on the chemistry of these reduced porphyrin derivatives, and their pi-cation radicals, demonstrate that this special class of compounds displays unique structural and magnetic properties.; The neutral and oxidized species are characterized by solution electronic spectra, including monitoring the appearance of absorption bands in the near-IR region of the electromagnetic spectrum. Other physical technique used in characterizing these complexes include IR, EPR, and Mossbauer spectroscopies. All complexes have been characterized by X-ray structure determinations. The metallo-beta-oxochlorin class has very distinct porphyrin ring to ring geometries. In the solid state, the metallo-beta-oxochlorins form laterally shifted dimeric units with larger center···center and metal···metal distances than those found in octaethylporphyrin pi-cation radicals.; Magnetic susceptibility techniques are powerful analytical tools that have the potential to provide important information regarding the magnetic behavior of inorganic complexes. Detailed descriptions involving techniques in collecting magnetic susceptibility data on metalloporphyrin complexes are provided.; The crystallographic characterization of the five-coordinate iron(II) oxochlorin complex, [Fe(oxoOEC)(NO)] is described. The high resolution structural data for [Fe(oxoOEC)(NO)], support that a tilt/bending of the axial NO ligand is an intrinsic feature of the bonding interactions in these complexes.; Substantial conformational diversity is reported in the porphyrin cores among various solvates of [Fe(OEP)(O2C2Cl3)]. The solvates include an unsolvated [Fe(OEP)(O2C2Cl 3)] structure, a chloroform solvate, [Fe(OEP)(O2C2Cl 3)]· CHCl3, and a trichloroacetic acid solvate. |
