Understanding the mechanisms governing temperature-dependent magnetic resonance properties is essential for enabling thermometry via magnetic resonance imaging. Herein we harness a new molecular design strategy for thermometry─that of effective mass engineering via deuteration in the first coordination shell─to reveal the mechanistic origin of 59Co chemical shift thermometry. Exposure of [Co(en)3]3+ (1; en = ethylenediamine) and [Co(diNOsar)]3+ (2; diNOsar = dinitrosarcophagine) to mixtures of H2O and D2O produces distributions of [Co(en)3]3+-dn (n = 0-12) and [Co(diNOsar)]3+-dn (n = 0-6) isotopomers all resolvable by 59Co NMR. Variable-temperature 59Co NMR analyses reveal a temperature dependence of the 59Co chemical shift, Δδ/ΔT, on deuteration of the N-donor atoms. For 1, deuteration amplifies Δδ/ΔT by 0.07 ppm/°C. Increasing degrees of deuteration yield an opposing influence on 2, diminishing Δδ/ΔT by -0.07 ppm/°C. Solution-phase Raman spectroscopy in the low-frequency 200-600 cm-1 regime reveals a red shift of Raman-active Co-N6 vibrational modes by deuteration. Analysis of the normal vibrational modes shows that Raman modes produce the largest variation in 59Co δ. Finally, partition function analysis of the Raman-active modes shows that increased populations of Raman modes predict greater Δδ/ΔT, representing new experimental insight into the thermometry mechanism.