Spectroscopic Signatures of Resonance Inhibition Reveal Differences in Donor-Bridge and Bridge-Acceptor Couplings.

The torsional dependence of the ground state magnetic exchange coupling () and the corresponding electronic coupling matrix element () for eight transition metal complexes possessing donor-acceptor (D-A) biradical ligands is presented. These biradical ligands are composed of an S = 1/2 metal semiquinone (SQ) donor and an S = 1/2 nitronylnitroxide (NN) acceptor, which are coupled to each other via -phenylene, methyl-substituted -phenylenes, or a bicyclo[2.2.2]octane ring. The observed trends in electronic absorption and resonance Raman spectral features are in accord with a reduction in electronic and magnetic coupling between D and A units within the framework of our valence bond configuration interaction model. Moreover, our spectroscopic results highlight different orbital mechanisms that modulate coupling in these complexes, which is not manifest in the ferromagnetic values. The work provides new detailed insight into the effects of torsional rotations which contribute to inhomogeneities in experimentally determined exchange couplings, electron transfer rates, and electron transport conductance measurements.