Effect of the alkyl chain length on the rotational dynamics of nonpolar and dipolar solutes in a series of N-alkyl-N-methylmorpholinium ionic liquids

Dinesh Chandra Khara, Jaini Praveen Kumar, Navendu Mondal, Anunay Samanta

Research output: Contribution to journalArticlepeer-review

69 Scopus citations

Abstract

Rotational dynamics of two dipolar solutes, 4-aminophthalimide (AP) and 6-propionyl-2-dimethylaminonaphthalene (PRODAN), and a nonpolar solute, anthracene, have been studied in N-alkyl-N-methylmorpholinium (alkyl = ethyl, butyl, hexyl, and octyl) bis(trifluoromethansulfonyl)imide (Tf2N) ionic liquids as a function of temperature and excitation wavelength to probe the microheterogeneous nature of these ionic liquids, which are recently reported to be more structured than the imidazolium ionic liquids (Khara and Samanta, J. Phys. Chem. B2012, 116, 13430-13438). Analysis of the measured rotational time constants of the solutes in terms of the Stokes-Einstein-Debye (SED) hydrodynamic theory reveals that with increase in the alkyl chain length attached to the cationic component of the ionic liquids, AP shows stick to superstick behavior, PRODAN rotation lies between stick and slip boundary conditions, whereas anthracene exhibits slip to sub slip behavior. The contrasting rotational dynamics of these probe molecules is a reflection of their location in distinct environments of the ionic liquids thus demonstrating the heterogeneity of these ionic liquids. The microheterogeneity of these media, in particular, those with the long alkyl chain, is further evidence from the excitation wavelength dependence study of the rotational diffusion of the dipolar probe molecules.

Original languageEnglish
Pages (from-to)5156-5164
Number of pages9
JournalJournal of Physical Chemistry B
Volume117
Issue number17
DOIs
StatePublished - 2 May 2013
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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