The oxidation potential of 2',3'-O-isopropylidene-5'-O-(tert-butyldimethysilyl)adenosine and its change upon pairing with the complementary base thymidine have been studied in chloroform solution by voltammetric methods. Differential pulse and cyclic voltammetry of an equimolar solution of the two nucleosides show two well-resolved peaks, which have been assigned to the formation of a H-bonded complex between the two nucleosides and to the fraction of unassociated adenosine in solution. No signal for thymidine oxidation has been detected. Equilibrium constants and enthalpy and entropy changes for self- and hetero-association in solution have been determined by NMR spectra. Quantum mechanical computations show that Hoogsteen and Watson-Crick association modes are of comparable stability in solution, and exhibit very similar oxidation potential in chloroform.