Nuclear singlet relaxation by chemical exchange

The population imbalance between nuclear singlet states and triplet states of strongly coupled spin-1/2 pairs, also known as nuclear singlet order, is well protected against several common relaxation mechanisms. We study the nuclear singlet relaxation of ¹³C pairs in aqueous solutions of 1,2-¹³C₂ squarate over a range of pH values. The ¹³C singlet order is accessed by introducing ¹⁸O nuclei in order to break the chemical equivalence. The squarate dianion is in chemical equilibrium with hydrogen-squarate (SqH^-) and squaric acid (SqH₂) characterized by the dissociation constants pK₁ = 1.5 and pK₂ = 3.4. Surprisingly, we observe a striking increase in the singlet decay time constants T_S when the pH of the solution exceeds ∼10, which is far above the acid-base equilibrium points. We derive general rate expressions for chemical-exchange-induced nuclear singlet relaxation and provide a qualitative explanation of the T_S behavior of the squarate dianion. We identify a kinetic contribution to the singlet relaxation rate constant, which explicitly depends on kinetic rate constants. Qualitative agreement is achieved between the theory and the experimental data. This study shows that infrequent chemical events may have a strong effect on the relaxation of nuclear singlet order.