We use density functional theory (DFT) calculations to show that oxygen vacancies (
) and mobility induce noncentrosymmetric polar structures in SrTi
Fe
Co
O
(STFC,
) with
, enhance the saturation magnetization, and give rise to large changes in the electric polarization
. We present an intuitive set of rules to describe the properties of STFC, which are based on the interplay between (Co/Fe)-
defects, magnetic cation coordination, and topological vacancy disorder. STFC structures consist of layered crystals with sheets of linearly organized O
-coordinated Fe–Co pairs, sandwiched with layers of O
-coordinated Ti. (Co/Fe)-
defects are the source of crystal distortions, cation off-centering and bending of the oxygen octahedra which, considering the charge redistribution mediated by
and the cations’ electronegativity and valence states, triggers an effective electric polarization. Oxygen migration for
leads to
>∼10 µC/cm
due to quantum-of-polarization differences between
structures. Increasing the oxygen deficiency to
yields
, the O migration of which resolved polarization for
is
3 µC/cm
. Magnetism is dominated by the Fe,Co spin states for
, and there is a contribution from Ti magnetic moments (∼1
) for
. Magnetic and electric order parameters change for variations of
or oxygen migration for a given oxygen deficiency. Our results capture characteristics observed in the end members of the series SrTi(Co,Fe)O
, and suggest the existence of a broader set of rules for oxygen-deficient multiferroic oxides.
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