The
torsional dependence of donor–bridge–acceptor
(D–B–A) electronic coupling matrix elements (<i><b>H</b></i><sub><i><b>DA</b></i></sub>, determined from the magnetic exchange coupling, <i><b>J</b></i>) involving a spin S<sub>D</sub> = 1/2 metal semiquinone
(Zn-<b>SQ</b>) donor and a spin S<sub>A</sub> = 1/2 nitronylnitroxide
(<b>NN</b>) acceptor mediated by the σ/π-systems
of <i>para</i>-phenylene and methyl-substituted <i>para</i>-phenylene bridges and by the σ-system of a bicyclo[2.2.2]octane
(<b>BCO</b>) bridge are presented and discussed. The positions
of methyl group(s) on the phenylene bridge allow for an experimentally
determined evaluation of conformationally dependent (π) and
conformationally independent (σ) contributions to the electronic
and magnetic exchange couplings in these D–B–A biradicals
at parity of D and A. The trend in the experimental magnetic exchange
couplings are well described by CASSCF calculations. The torsional
dependence of the pairwise exchange interactions are further illuminated
in three-dimensional, “Ramachandran-type” plots that
relate D–B and B–A torsions to both electronic and exchange
couplings. Analysis of the magnetic data shows large variations in
magnetic exchange (<i><b>J</b></i> ≈ 1–175
cm<sup>–1</sup>) and electronic coupling (<i><b>H</b></i><sub><i><b>DA</b></i></sub> ≈ 450–6000
cm<sup>–1</sup>) as a function of bridge conformation relative
to the donor and acceptor. This has allowed for an experimental determination
of both the σ- and π-orbital contributions to the exchange
and electronic couplings