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Excimer formation of 6-(1-pyrenyl)hexyl-11(1-pyrenyl)undecanoate within an ionic liquid and cosolvent-modified ionic liquid mixture.
MedLine Citation:
PMID:  23299179     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The ring closing metathesis within an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF(6)]), a 'green' solvent tetraethylene glycol (TEG), and their equimolar mixture is investigated through the intramolecular excimer formation of 6-(1-pyrenyl)hexyl-11-(1-pyrenyl)undecanoate []. The excimer formation efficiency correlates directly with the inverse of the bulk viscosity of the systems. A simplistic double exponential decay model based on Birk's scheme is enough to fit the excited state intensity decay of in these liquids. This behavior is in stark contrast to that reported in organic solvents and in scCO(2), where three exponentials are required to fit the fluorescence decay. The activation energies of the excimer formation (E(a)), viscous flow (E(a,η(bulk))), and microviscosity (E(a,η(μ))) were estimated from the temperature dependence. E(a) and E(a,η(μ)) are significantly higher for the equimolar mixture as compared to that for [bmim][PF(6)] or TEG, whereas E(a,η(bulk)) is close to the average. This highlights the important outcome that the cyclization dynamics scales with the microviscosity rather than the bulk viscosity of the systems investigated.
Authors:
Rewa Rai; Siddharth Pandey
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2013-1-9
Journal Detail:
Title:  Physical chemistry chemical physics : PCCP     Volume:  -     ISSN:  1463-9084     ISO Abbreviation:  Phys Chem Chem Phys     Publication Date:  2013 Jan 
Date Detail:
Created Date:  2013-1-9     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  100888160     Medline TA:  Phys Chem Chem Phys     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, 110016, India. sipandey@chemistry.iitd.ac.in.
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