Effect of electrolyte on ground and excited state properties of a ketocyanine dye in non-aqueous solvents

Ray, Narayan; Basu, Jayanta Kumar; Shannigrahi, Mrinmoy; Bagchi, Sanjib

doi:10.1016/j.cplett.2005.01.039

Cited by 19 publications

(17 citation statements)

References 24 publications

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“…Because there is no formation of J-aggregates, these decay times are attributed to the monomeric form of TDBC. The major component of the decay (1.2–1.4 ns) is similar to those reported for cyanine dyes in the literature. − As aqueous NaOH (final [NaOH] = 1.7 M, water = 30 wt %) is added to glyceline/reline, the 1.2–1.4 ns (major component) decay time decreases dramatically to the subnanosecond scale (Figure and Table ). This can be perceived to be due to the formation of J-aggregates because any aggregation or dye-adduct interaction usually results in a reduced lifetime. − …”

Section: Results and Discussionsupporting

confidence: 83%

Aggregation of Carbocyanine Dyes in Choline Chloride-Based Deep Eutectic Solvents in the Presence of an Aqueous Base

2017

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Deep eutectic solvents (DESs) have shown potential as novel media to support molecular aggregation. The self-aggregation behavior of two common and popular carbocyanine dyes, 5,5',6,6'-tetrachloro-1,1'-diethyl-3,3'-di(4-sulfobutyl)-benzimidazole carbocyanine (TDBC) and 5,5'-dichloro-3,3'-di(3-sulfopropyl)-9-methyl-benzothiacarbo cyanine (DMTC), is investigated within DES-based systems under ambient conditions. Although TDBC is known to form J-aggregates in basic aqueous solution, DMTC forms H-aggregates under similar conditions. The DESs used, glyceline and reline, are composed of salt choline chloride and two vastly different H-bond donors, glycerol and urea, respectively, in 1:2 mol ratios. Both DESs in the presence of base are found to support J-aggregates of TDBC. These fluorescent J-aggregates are characterized by small Stokes' shifts and subnanosecond fluorescence lifetimes. Under similar conditions, DMTC forms fluorescent H-aggregates along with J-aggregates within the two DES-based systems. The addition of cationic surfactant cetyltrimethylammonium bromide (CTAB) below its critical micelle concentration (cmc) to a TDBC solution of aqueous base-added glyceline shows the prominent presence of J-aggregates, and increasing the CTAB concentration to above cmc results in the disruption of J-aggregates and the formation of unprecedented H-aggregates. DMTC exclusively forms H-aggregates within a CTAB solution of aqueous base-added glyceline irrespective of the surfactant concentration. Anionic surfactant, sodium dodecylsulfate (SDS), present below its cmc within aqueous base-added DESs supports J-aggregation by TDBC; for similar SDS addition, DMTC forms H-aggregates within the glyceline-based system whereas both H- and J-aggregates exist within the reline-based system. A comparison of the carbocyanine dye behavior in various aqueous base-added DES systems to that in aqueous basic media reveals contrasting aggregation tendencies and/or efficiencies. Surfactants as additives are demonstrated to control and modulate carbocyanine dye self-aggregation within DES-based media. The unique nature of DESs as alternate media toward affecting cyanine dye aggregation is highlighted.

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Section: Results and Discussionsupporting

confidence: 83%

Aggregation of Carbocyanine Dyes in Choline Chloride-Based Deep Eutectic Solvents in the Presence of an Aqueous Base

2017

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“…Values of K, ε S (λ) and ε M (λ) that give the best fit to eq 7 in the least-squares sense were determined, by a linear regression analysis. The equilibrium constant for the interaction between the dye in the excited state and the lithium ion was determined by a method described earlier . The observed maximum fluorescence energy, E (F), can be considered as mole fraction average of E S and E M , the maximum fluorescence energy of the two species, viz., the solvated and complexed forms of the dye. − Thus, one gets Equation 8 can be rearranged to give where K 1 is the equilibrium constant for the following process…”

Section: Methodsmentioning

confidence: 99%

“…In our laboratory we have studied solvation interaction of these dyes in pure, mixed binary and ternary solvents and also in various microheterogeneous media by using the fluorescence parameters. In a recent communication we have reported a preliminary study on the effect of electrolytes on ground- and excited-state properties of a ketocyanine dye . It has been observed that the Li + ion in aprotic solvents brings about a significant change in spectral properties.…”

Section: Introductionmentioning

confidence: 99%

Lithium Ion−Ketocyanine Dye Interactions in the Ground and Excited States

2006

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Electronic absorption and emission spectral characteristics of a ketocyanine dye have been studied in solution in the presence of lithium perchlorate. Absorption spectral studies indicate complex formation between lithium ion and the dye in the ground state. The value of the equilibrium constant along with the molar absorbance of the absorbing species has been determined for the dye-cation interaction. The energy of maximum fluorescence shifts toward the red with the addition of LiClO(4). Steady-state emission studies point to the existence of two emitting species, viz., the solvated and the complexed dye in equilibrium. The values of the equilibrium constant for the process have been determined in acetone and acetonitrile. Time-resolved studies in the picosecond domain in pure solvents reveal that the lifetime (tau) value increases as the solvation interaction increases. Time-resolved studies also indicate the presence of two emitting species in equilibrium.

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“…These compounds are also used as laser dyes and have industrial application in polymer imaging system [15][16][17]. Recent experimental observations suggest a significant change in absorption spectra due to the formation of complex involving the dye and metal ions [18][19][20][21][22]. It has also been observed that interactions of these dyes with cations in acetonitrile solution cause a substantial shift of absorption and fluorescence maxima indicating the formation of dye-cation complexes in the ground and excited state.…”

Section: Introductionmentioning

confidence: 99%

Electronic spectra and (hyper)polarizabilities of ketocyanine dye complexes with metal ions

Das¹,

Sardar²,

Bagchi³

2013

Journal of Molecular Structure

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Effect of electrolyte on ground and excited state properties of a ketocyanine dye in non-aqueous solvents

Cited by 19 publications

References 24 publications

Aggregation of Carbocyanine Dyes in Choline Chloride-Based Deep Eutectic Solvents in the Presence of an Aqueous Base

Aggregation of Carbocyanine Dyes in Choline Chloride-Based Deep Eutectic Solvents in the Presence of an Aqueous Base

Lithium Ion−Ketocyanine Dye Interactions in the Ground and Excited States

Electronic spectra and (hyper)polarizabilities of ketocyanine dye complexes with metal ions

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