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

Ana Pérez; Diana de Saá; Alfredo Ballesteros; José Luis Serrano; Teresa Sierra; Pilar Romero

doi:10.1002/chem.201204604

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

Chemistry. 2013 Jul 29;19(31):10271-9. doi: 10.1002/chem.201204604. Epub 2013 Jun 20.

Authors

Ana Pérez¹, Diana de Saá, Alfredo Ballesteros, José Luis Serrano, Teresa Sierra, Pilar Romero

Affiliation

¹ Instituto de Nanociencia de Aragón, Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza, Spain.

PMID: 23787768
DOI: 10.1002/chem.201204604

Abstract

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.

Keywords: DOSY; NMR spectroscopy; aggregation; self-assembly; thermodynamics.