Supporting Information for the article entitled, ‘Excited state intramolecular charge transfer reaction in non-aqueous reverse micelles: Effects of Solvent Confinement and Electrolyte Concentration’ by
Tuhin Pradhan, Harun Al Rasid Gazi, Biswajit Guchhait and Ranjit Biswas[(]
Department of Chemical, Biological & Macromolecular Sciences, and Unit for Nanoscience & Technology, S. N. Bose National Centre for Basic Sciences, JD Block, Sector III, Salt Lake, Kolkata 700 098, INDIA
Table S2: Experimentally measured solvation response functions at different electrolyte (LiClO4) concentrations in AOT/n-heptane/ acetonitrile reverse micelles at room temperature: Fit parametersa
Conc.(M) / / / / /0.1 / 33 / 435 / 46.8 / 53.2 / 47.2
0.25 / 70 / 526 / 24.3 / 75.7 / 18.6
0.4 / 69 / 526 / 19.1 / 81.2 / 35.0
0.5 / 79 / 500 / 4.6 / 95.4 / 10.0
0.75 / 64 / 500 / 35.0 / 64.6 / 34.7
0.9 / 12 / 500 / 44.6 / 55.4 / 44.8
a) These numbers are better within 10% of the reported values (estimated based on limited data sets).The estimated missing components are obtained by using the Fee-Maroncelli method described in Ref.51
Table S3: Anisotropy decay parameters for C-153 in AOT/n-heptane/ acetonitrile reverse micelles at Ws = 5 in presence of LiClO4. Excitation wavelength used is 375 nm, IRF ~ 75 ps. Corresponding values of estimated viscosity (in centipoises) are also summarized.
Conc.(M) / / / / / / / /0 / 17 / 388 / 89.49 / 10.51 / 56 / 0.32 / 1.06 / 0.96
0.05 / 15 / 603 / 93.06 / 6.94 / 56 / 0.34 / 1.04 / 0.96
0.1 / 31 / 784 / 96.57 / 3.43 / 57 / 0.36 / 1.38 / 0.98
0.25 / 23 / 376 / 88.28 / 11.72 / 64 / 0.25 / 1.12 / 1.10
0.4 / 16 / 675 / 90.88 / 9.11 / 76 / 0.33 / 1.05 / 1.32
0.5 / 16 / 661 / 90.5 / 9.5 / 77 / 0.33 / 1.05 / 1.35
0.75 / 19 / 833 / 89.9 / 10.1 / 101 / 0.30 / 1.1 / 1.78
0.9 / 17 / 989 / 93.12 / 6.88 / 84 / 0.33 / 1.13 / 1.47
Table S5: Peak frequency and band width associated with absorption spectra and LE band a in AOT/n-heptane/acetonitrile and AOT/n-heptane/methanol reverse micelles.
(A) P5C :
ACN / MeOH1 / 27.91 / 1.04 / 28.10 / 0.71
2 / 27.82 / 1.11 / 28.11 / 0.75
3 / 27.74 / 1.13 / 28.07 / 0.89
4 / 27.68 / 1.17 / 28.08 / 0.88
5 / 27.66 / 1.26 / 28.03 / 1.00
8 / 27.99 / 1.10
10 / 27.96 / 1.18
(B) P6C :
ACN / MeOH1 / 28.23 / 0.79 / 28.34 / 0.65
2 / 28.20 / 0.91 / 28.34 / 0.70
3 / 28.13 / 0.96 / 28.31 / 0.81
4 / 28.08 / 0.99 / 28.30 / 0.83
5 / 28.02 / 1.04 / 28.26 / 0.94
8 / 28.23 / 0.96
10 / 28.16 / 1.22
(C) M6C :
ACN / MeOH1 / 28.24 / 0.97 / 28.32 / 1.12
2 / 28.25 / 1.11 / 28.37 / 1.11
3 / 28.21 / 1.13 / 28.34 / 1.15
4 / 28.16 / 1.14 / 28.34 / 1.18
5 / 28.09 / 1.09 / 28.31 / 1.23
8 / 28.25 / 1.36
10 / 28.21 / 1.43
a Peak frequencies (ν) and band widths (Γ, fwhm) are in units of 103 cm-1
Figure Captions
Fig.S1: Absorption (upper panel) and emission (lower panel) spectra of C153 in AOT/heptane/acetonitrile reverse micelles at values 1, 3 and 5. Absorption and emission spectra of C153 in heptane and acetonitrile (“ACN”) are also shown. All representations are color-coded.
Fig.S4: Absorption spectra of P6C in AOT/heptane/acetonitrile at values 1, 3 and 5. Absorption and emission spectra of P6C in heptane and acetonitrile (“ACN”) are also shown. All representations are color-coded.
Fig.S6: Electrolyte (LiClO4) concentration dependence of peak frequencies () and emission bandwidths () of CT and LE fluorescence emission bands of P5C, P6C and M6C in AOT/n-heptane/acetonitrile at Ws = 5. Circles, hexagons and squares represent data for M6C, P6C and P5C, respectively.
Fig.S7: dependence of reaction time constant () associated with the LECT conversion reaction of P5C, P6C and M6C in AOT/n-heptane/ acetonitrile (upper panel) and AOT/n-heptane/methanol reverse micelles (lower panel). Note that the squares, hexagons, circles represent data respectively for P5C, P6C and M6C. Error associated with the reaction time constants is typically of the reported values.
Fig. S1
Fig. S4
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