We report on a certain class of three-dimensional topological insulators and semimetals protected by spinless 𝒫⁢𝒯 symmetry, hosting an integer-valued bulk invariant. We show using homotopy arguments that these phases host multigap topology, providing a realization of a single ℤ invariant in three spatial dimensions that is distinct from the Hopf index. We identify this invariant with the Pontryagin index, which describes Belavin-Polyakov-Schwartz-Tyupkin (BPST) instantons in particle physics contexts and corresponds to a three-sphere winding number. We study naturally arising multigap linked nodal rings, topologically characterized by split-biquaternion charges, which can be removed by non-Abelian braiding of nodal rings, even without closing a gap. We additionally recast the describing winding number in terms of gauge-invariant combinations of non-Abelian Berry connection elements, indicating relations to Pontryagin characteristic class in four dimensions. These topological configurations are furthermore related to fully nondegenerate multigap phases that are characterized by a pair of winding numbers relating to two isoclinic rotations in the case of four bands and can be generalized to an arbitrary number of bands. From a physical perspective, we also analyze the edge states corresponding to this Pontryagin index as well as their dissolution subject to the gap-closing disorder. Finally, we elaborate on the realization of these novel non-Abelian phases, their edge states, and linked nodal structures in acoustic metamaterials and trapped-ion experiments.