Experimental and Theoretical Investigation of a Series of Novel Dimanganese(III) μ-Hydroxo Bisporphyrins: Magneto-Structural Correlation and Effect of Metal Spin on Porphyrin Core Deformation.

The synthesis, structure, and properties of a new family of five ethane-bridged dimanganese(III) μ-hydroxo bisporphyrins with the same core structure but different counteranions are reported here. Additions of 10% Brønsted acids such as HI, HBF4, HSbF6, HPF6, and HClO4 to a dichloromethane solution of the dichloro dimanganese(III) bisporphyrin produces complexes having a remarkably bent μ-hydroxo group with I3(-), BF4(-), SbF6(-), PF6(-), and ClO4(-) as counteranions, respectively. The X-ray structures of all complexes have been determined, which have revealed the presence of two equivalent high-spin manganese(III) centers with equally distorted porphyrin rings in the complexes, in sharp contrast with the case for the diiron(III) μ-hydroxo bisporphyrin analogues. (1)H NMR spectra have shown highly deshielded meso resonances, unlike the case for the diiron(III) analogues, where the meso resonances are highly shielded. The variable-temperature magnetic data have been subjected to a least-squares fit which provides a moderate antiferromagnetic coupling through the hydroxo bridge between two zero-field split Mn(III) centers with coupling constant (J) values ranging from -29.5 to -38.6 cm(-1). Fairly good correlations are observed for J with Mn-O(H) distances and Mn-O(H)-Mn angles for all the complexes except for that having an I3(-) counteranion. DFT calculations support the stabilization of two equivalent high-spin Mn(III) porphyrin cores in the complexes and have also explored the role of metal spin in controlling porphyrin ring deformation. Unlike diiron(III) μ-hydroxo bisporphyrin complexes, the dimanganese(III) analogues do not have easily accessible spin states of the metal attainable by subtle environmental perturbations and, therefore, can only stabilize the high-spin state with a variety of counteranions.