Communication

Fibers and Polymers 2008, Vol.9, No.5, 659-660

Solvatochromism of Indonaphthol Dye

Jin-Seok Bae, Young-A Son1, and Sung-Hoon Kim*
Department of Textile System Engineering, Kyungpook National University, Daegu 702-701, Korea
1
Department of Organic Materials and Textile System Engineering, Chungnam National University, Daejeon 305-764, Korea
(Received April 7, 2008; Revised May 16, 2008; Accepted June 2, 2008)

Abstract: The solvatochromic behavior of indonaphthol dye was described. The UV/Vis absorption spectra of this com-
pound have been studied in 5 solvents of different polarity. The solvatochromism of indonaphthol dye is discussed with the
aid of semiempirical calculations.
Keywords: Indonaphthol dye, Solvatochromism, Solvent polarity, ET

Solvatochromism can be defined as the phenomenon
whereby a compound changes color, either by a change in
the absorption or emission spectra of the molecule, when
dissolved in different solvents. Solvatochromic effects are best
monitored by means of UV/VIS spectroscopy. A hypsochromic
shift of the UV/VIS absorption band, with increasing solvent
polarity is usually called negative solvatochromism. The
corresponding bathochromic shift, with increasing solvent
polarity is termed positive solvatochromism. Solvatochromic
dyes are suitable as probes for the determination of solvent
polarity.
Intramolecular charge-transfer (CT) chromophores can be
defined as chromophores in which movement of π-electron
density from the donor to acceptor accompanies the 1st
excitation. The values show the intramolecular CT character
of indonaphthol; that is, the aniline moiety acts as a donor
and the naphthoquinoneimine moiety acts as an acceptor.
The electronic absorption spectra of indonaphthol was
observed in various solvents. The absorption maximum
wavelength (λmax) of the intramolecular charge-transfer band
shifted from 593 nm (in ethanol) to 533 nm (in hexane)
(Figure 2).
The extraordinarily large negative solvatochromic Reichardt’s
betain dye (2,6-diphenyl-4-(2,4,6-triphenyl-N-pyridino)phenolate)
has been used to established UV/Vis spectrophotometrically

Figure 1. π-Electron density changes for 1st excitation of

indonaphthol dye (○: −, ●: +).
Indonaphthol dyes are blue in color and are typical donor-
acceptor chromogens. The indoaniline dye can be prepared
by condensing α-naphthol with p-nitroso-dimethylaniline,
or by the oxidation (e.g. with dichromate and acetic acid) or
a mixture of α-naphthol and p-aminodimethylaniline. We
have previously reported the synthesis and X-ray structural
characterization of indoaniline dyes [1-3]. Such indoaniline
dyes are solvent soluble dyes which are not now used for
textile coloration, but enjoy usage in color photography and
also serve as intermediates for sulfur dyes.
For the basic structure of indonaphthol, the π-electron density
changes accompanying the 1st transition have been calculated
using Pariser-Parr-Pople molecular orbital (PPP MO) method
(Figure 1).
Figure 2. Absorption spectra of indonaphthol in different solvent;
*Corresponding author: shokim@knu.ac.kr (1) ethanol, (2) DMF, (3) chloroform, (4) toluene, and (5) hexane.

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Figure 3. Correlations between the ET values and λmax of indonaphthol
dye.
Figure 4. Effect of solvent polarity on the transition energy of
indonaphthol dye.
derived empirical parameters of solvent polarity, known as
ET values [4,5]. Reichardt and co-workers determined ET
values (expressed in kcal mol−1) for ca. 300 solvents or
solvent mixtures, with values ranging from 63.1 (H2O) to
30.9 (hexane). In this present work, reasonably linear plots
were obtained on plotting λmax versus the solvent parameter
ET (Figure 3).
As the solvent polarity increased, a bathochromic shift
was observed (i.e., positive solvatochromism). The positive
solvatochromism indicated that the indonaphthol dye have a
large dipole moment in the excited state than in the ground
state. Calculated dipole moment (μ, Debye) in the ground
state and first excited singlet states are presented in Figure 4.
The use of the quantum chemical DMol3 approach for the
interpretation of the electronic transitions and electronic
structure of indoaniline dye allows a prediction to be made
of the spectroscopic differences in different solvents. All the
theoretical calculations were performed by DMol3 program
Jin-Seok Bae et al.
Figure 5. Electron distribution of the HOMO and LUMO energy
levels of the indoaniline dye.
in the Materials Studio 4.2 package [6,7] which is the
quantum mechanical code using density functional theory.
Perdew-Burke-Ernzerhof (PBE) function of generalized gradient
approximation (GGA) level [8] with double numeric polarization
basis set [4] was used to calculate the energy level of the
frontier molecular orbital.
Figure 5 shows the calculated molecular structure of the
dye and the electron distribution of its HOMO and LUMO.
Comparison of the electron distribution in the frontier MOs
reveals that HOMO-LUMO excitation moved the electron
distribution from aniline moiety to the naphthquinoneimine
moiety, which show a strong migration of intramolecular
charge-transfer character of indoaniline dye. The redistribution
of the electron density during the HOMO-LUMO electron
transition determines the influence on the color properties of
indoaniline dye.
Acknowledgement
This research was supported by Kyungpook National
University Research Fund, 2007.
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