We present DFT predictions (CAM-B3LYP/II level) for the paramagnetic Nuclear Magnetic Resonance (pNMR) spectra of small molecular models based on the Cu(II)-paddlewheel dimer motif that is present in metal–organic frameworks (MOFs, notably the HKUST and STAM families). We explore potential point defects with spin–1/2 discovered through electron paramagnetic resonance (EPR) experiments. We consider defects through substitution of one Cu(II) centre in the dimer with protons, or through one-electron reduction, affording a mixed-valence dimer. While most of the defects have predicted pNMR shifts at room temperature in the range of those for the non-defective MOFs, their detection and assignment should be possible based on their distinct temperature dependence.