The low-lying structures of the self-conjugate (N=Z) nuclei <sup>82</sup><sub>41</sub>Nb<sub>41</sub> and <sup>86</sup><sub>43</sub>Tc<sub>43</sub> have been investigated using isomeric-decay spectroscopy following the projectile fragmentation of a <sup>107</sup>Ag beam. These represent the heaviest odd–odd N=Z nuclei in which internal decays have been identified to date. The resulting level schemes shed light on the shape evolution along the N=Z line between the doubly-magic systems <sup>56</sup><sub>28</sub>Ni and <sup>100</sup><sub>50</sub>Sn and support a preference for T=1 states in Tz=0 odd–odd nuclei at low excitation energies associated with a T=1 neutron–proton pairing gap. Comparison with Projected Shell Model calculations suggests that the decay in <sup>82</sup>Nb may be interpreted as an isospin-changing K isomer
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