NMR spectroscopic study of the self-aggregation of 3-hexen-1,5-diyne derivatives

The self-assembly of polycatenar molecules derived from 1,6-diphenyl-3,4-dipropyl-3-hexen-1,5-diyne has been studied in detail by solution NMR spectroscopy. The analysis of the concentration- and temperature-dependent evolution of the chemical shifts and the diffusion coefficients in [D12]cyclohexane agrees well with an isodesmic model of association in this solvent. The association constants for the stacking and entropy and enthalpy of the process have been obtained. The driving force for the aggregation process is provided by a negative enthalpy (ΔH), which is partially compensated by a negative entropy (ΔS). A structural study of the self-assembly in solution has been carried out with the help of NOESY NMR spectroscopic experiments. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.This work was supported by the CICYT projects MAT2009-14636-C03-01, MAT2011-27978-C02-02, CTQ2009-15611-C02-01, FC-11COF11-17, Marie Curie Action ITN no. 215884-2, FEDER funding (EU) and the Aragon Government.Peer Reviewe