Controlling the formation of cyanine dye H- and J-aggregates with cucurbituril hosts in the presence of anionic polyelectrolytes

Suresh Gadde, Elizabeth K. Batchelor, Angel Kaifer

Research output: Contribution to journalArticle

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Abstract

The presence of anionic polyelectrolytes enhances the tendency of cationic cyanine dyes to form aggregates in aqueous media. In this work we investigate the interactions between two cyanine dyes, pseudoisocyanine (PIC) and pinacyanol (PIN), with polystyrenesulfonate (PSS) as the key additive to develop J- and H-aggregates. We also take advantage of the binding properties of the cucurbit[7]uril (CB7) host to control formation of these aggregates through its host-guest interactions with the dye molecules. UV/Vis absorption spectroscopic studies clearly demonstrate the PSS-enhanced formation of J-aggregates in the case of PIC and H-aggregates in the case of PIN. Electrostatic interactions between the cyanine dye molecules and the polyelectrolyte chains assist the formation of J- or H-aggregates at very low dye concentrations (ca. 10 μm). Optimum development of dye aggregates was observed at a sulfonate/dye molar ratio of about 3:1. Departures from this stoichiometric ratio seem to perturb the optimal aggregate structure. Furthermore, the presence of CB7 was found to effectively disrupt the interactions responsible for dye aggregation. Thus, CB7 completely disrupts the J-aggregates formed by PIC and the H-aggregates (as well as lower concentrations of J-aggregates) formed by PIN. UV/Vis and emission spectroscopic studies clearly indicate that binding of CB7 to both dye molecules removes them from the aggregate structures. Our spectroscopic data clearly indicate that regulation of the relative molar ratios of dye, CB7 host, and polyelectrolyte sulfonate groups leads to a quantitative control of dye aggregation, yielding variable amounts of PIC J- and PIN Haggregates in these solutions.

Original languageEnglish
Pages (from-to)6025-6031
Number of pages7
JournalChemistry - A European Journal
Volume15
Issue number24
DOIs
StatePublished - Jun 8 2009

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Polyelectrolytes
Coloring Agents
Dyes
Molecules
cucurbituril
Agglomeration
Coulomb interactions

Keywords

  • Aggregation
  • Cucurbiturils
  • Cyanines
  • Supramolecular chemistry

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Controlling the formation of cyanine dye H- and J-aggregates with cucurbituril hosts in the presence of anionic polyelectrolytes. / Gadde, Suresh; Batchelor, Elizabeth K.; Kaifer, Angel.

In: Chemistry - A European Journal, Vol. 15, No. 24, 08.06.2009, p. 6025-6031.

Research output: Contribution to journalArticle

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AB - The presence of anionic polyelectrolytes enhances the tendency of cationic cyanine dyes to form aggregates in aqueous media. In this work we investigate the interactions between two cyanine dyes, pseudoisocyanine (PIC) and pinacyanol (PIN), with polystyrenesulfonate (PSS) as the key additive to develop J- and H-aggregates. We also take advantage of the binding properties of the cucurbit[7]uril (CB7) host to control formation of these aggregates through its host-guest interactions with the dye molecules. UV/Vis absorption spectroscopic studies clearly demonstrate the PSS-enhanced formation of J-aggregates in the case of PIC and H-aggregates in the case of PIN. Electrostatic interactions between the cyanine dye molecules and the polyelectrolyte chains assist the formation of J- or H-aggregates at very low dye concentrations (ca. 10 μm). Optimum development of dye aggregates was observed at a sulfonate/dye molar ratio of about 3:1. Departures from this stoichiometric ratio seem to perturb the optimal aggregate structure. Furthermore, the presence of CB7 was found to effectively disrupt the interactions responsible for dye aggregation. Thus, CB7 completely disrupts the J-aggregates formed by PIC and the H-aggregates (as well as lower concentrations of J-aggregates) formed by PIN. UV/Vis and emission spectroscopic studies clearly indicate that binding of CB7 to both dye molecules removes them from the aggregate structures. Our spectroscopic data clearly indicate that regulation of the relative molar ratios of dye, CB7 host, and polyelectrolyte sulfonate groups leads to a quantitative control of dye aggregation, yielding variable amounts of PIC J- and PIN Haggregates in these solutions.

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