Photophysics of indole derivatives:

Experimental resolution of L and Lb transitions

and comparison with theory
Maurice R. Eftink*, LeRoy A. Selvidge Patrik R. Callis,
and Aden A. Rehms
*Depfjj.tment of Chemistry, University of Mississippi, University, MS 38677 and 4Department of Chemistry,
Montana State University, Bozeman, MT 59717

Abstract
Fluorescence excitation and anisotropy spectra are presented for a set of methyl and methoxyindoles at -50C
in propylene glycol glass. These spectra are interpreted in terms of two overlapping ii electronic
transitions ('La and 'L). Semiempirical molecular orbital calculations are presented to correlate with the
observed spectral changes caused by methyl and methoxy substitution.

1. INTRODUCTION low temperature fluorescence anisotropy and excitation

The luminescence of tryptophan has been widely
used to study various kinetic and structural aspects of
proteins (1, 2, 3). For this reason a thorough under-
standing of the photophysics of indole is of great
importance. The accepted description of the photo-
physics of indole is in terms of two overlapping it
7* transitions, referred to by the Platt labels 'L and
'Lb (2, 4, 5, 6, 7). From studies of the angular
dependence of the absorbance of UV light by oriented
crystals of indole, Yamamoto and Tanaka (6) deter-
mined that the 'La and 'Li, transition moments are
approximately orthogonal to one another in the plane
of the ring. From measurements of the low tempera-
ture fluorescence anisotropy of indole, Valeur and
Weber (5) were able to resolve the excitation spectra
for the 'La and 'Li, components.
The 'La transition is found to be much more
sensitive to its environment than the 1J transition.
In the vapor phase the 'Li, excited state is lowest in
energy for most indole derivatives, but in polar
solvents, the 'La excited state is preferentially
stabilized and the latter becomes the lowest excited
singlet state (8-12). The greater interaction, between
the 'La transition and polar solvent molecules, is
attributed to a much larger change in permanent
dipole moment associated with excitation to the 'La
state.
In addition to their different solvent dependencies,
the 'La and 'Lb transitions are thought to have
different vibronic patterns. The 'Lb absorption appears
to have a strong 0 - 0 transition, with less intense
vibronic peaks at higher energy. The 'L absorption
appears to be broad and featureless (5, 6).
If this model of the photophysics of indole is valid,
it should also be able to describe the photophysics of
simple derivatives of indole (8,10,13,14). Here we
present studies of the photophysics of a thrge set of
methyl and methoxy indole derivatives. We present
both experimental and theoretical studit of the effect
of these substitutions. Specifically, we have obtained
spectra for these derivatives, and, using the arguments
of Valeur and Weber (5), we have attempted to resolve
the 'La and 'Lb transitions. The questions addressed
are whether methyl or methoxy substitutions change
the electronic/spectral character of indole (i.e., the
relative energy level, strength, vibronic structure, or
angular separation of the 'La and 'Lb transition
moments). We compare experimental results with
molecular orbital calculations for the derivatives to see
if the observed spectral features can be predicted.
2. MATERIALS AND METHOD
2.1 Materials: Indole ard its various methyl
and methoxy derivatives were obtained from Aldrich
or Sigma Chemical Co. Indole, 2-methylindole, 3-
methylindole, 2,3-dimethylindole, and 5-methoxyindole
were sublimed before use. 1-Methylindole was vacuum
distilled before use. L-Tryptophan was recrystallized
from water. All other compounds were used without
further purification. Spectral grade 1,2-propanediol
(PPG) was obtained from Aldrich Chemical Co.
2.2 Ex ' erimental Methods: Low
temperature (-50C) fluorescence excitation spectra and
anisotropy data were obtained with an SLM 4800
fluorometer, equipped with a Dewar flask having a
quartz finger. Excitation spectra were corrected for
the lamp profile. See reference (15) for further
experimental details.
2.3 Theoretical Methods: Semiempirical
SCFMO-CI calculations were performed using an
INDO/S (16) package obtained from Dr. Michael
Zerner, University of Florida (16,17). At least three
calculations were performed for each molecule: (A)
about 25 singly excited and 170 doubly excited ivir*
configurations were used with Ohno-Klopman (OK)
repulsion integrals, hereafter referred to as the SDCI
basis; (B) 196 singly excited configurations arising
from all possible promotions from the 14 highest
occupied MO's (HOMO's) to the 14 lowest unoccupied
MO's (LUMO's) using Mataga-Nishimoto (MN) electron
repulsion integrals, hereafter referred to as the SCI

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 basis; (C) same as (B) except 200 singly excited
configurations which were those possible using the 10
HOMO's and 20 LUMO's. The geometry chosen for
the indole frame was that found from the tryptophan
crystal structure (18), except that the N-H and C-H
bond lengths were taken as 1.08A. When methyls
were substituted for hydrogens a C-C bond length of
1.52A was used; for methoxy substitution the ring C-
o length was taken to be 1.36A and methyl C-O
length was taken to be 1.43A. The C-O-C bond angle
was always 120.
3. EXPERIMENTAL RESULTS
Shown in Figures 1 and 2 are fluorescence
excitation and anisotropy spectra (broad band
emission) for indole, methylindoles and methoxyindoles
in frozen (-50C) solutions of propylene glycol (PPG).
In Figures 3 and 4 are shown the emission wave-
length dependence of the anisotropy values, for
different excitation wavelengths.

>
rL
0
a:
F-
0
(1)
z
>-
F
Ci)
z
LU
z
F

WAVELENGTH nm
Figure 1. Fluorescence excitation spectra (solid lines) and anisotropy spectra (solid lines, lighter ink) of indole and
methyl indoles in PPG at -50C. Resolutions into L (....) and Lb (---) spectra are shown. See text for details.

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 3.1 Methylindoles: The methylindoles (Figure
1) all show excitation spectra which are similar to that
for indole. That is, for most derivatives a peak is
seen near 287-291 run, which corresponds (see below)
to the 0-0 transition of the 'Lb oscillator. 1-Methyl
and 5-methylindole are distinct in having this 0-0 'Lb
transition at a longer wavelength of 295 nm. Some
methylindoles, particularly 3-methylindole and 2,3-
dimethylindole, show strong, slowly rising absorbance
above 300 nm, due to the 'La transition (see below).
The anisotropy spectra of most methylindoles
appear similar to that of indole, itself. A plateau
between r = 0.30 - 0.35 is seen at wavelengths at or
above 300 nm. This plateau has been interpreted as
resulting from selective excitation into the 'L transi-
tion of indole (4,5). A dip is seen in the 287-291
nm region, corresponding to the peak in the excitation
spectra (the 0-0 Lb transition). For 1-methyl and 5-
methylindole the 'Lb peak (295 nm) in the excitation
spectrum does not correspond to a dip in the
anisotropy spectrum. For 1-methylindole there is a
dip in the anisotropy spectrum, but it clearly occurs at
a lower wavelength (292 nm). As we will argue later,
the Lb oscillator appears to be the lowest in energy (or
to be of nearly equal energy to the L) in 1-methyl
and 5-methylindole.
The emission wavelength dependence of the
anisotropy values for the methylindoles is shown in
Figure 3. For indole, 2-, 3-, and 6-methyl-, and 2,3-
dimethylindole, the anisotropy values decrease or
increase very slightly between 300 and 380 nm, and
the gradual trends are similar at different excitation

>-
00
F-
0
C/)
z
(I)
z
LU
zF-
320
WAVELENGTH , nm
>- 0.
00
F-
0U) 0.30
z
0.1
U)
zLi
zF- 0.
240 260 280 300 320 260 280 300 320
WAVELENGTH, nm
Figure 2. Fluorescence excitation spectra (solid lines) and anisotropy spectra (solid lines, lighter ink) of indole and
methoxyindoles in PPG at -50C. Resolutions into L (....) and Lb (---) spectra are shown.

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 290 320 350 380290 320 350 320
0.35 - 380290 350 310

0.25 Indole
_; .
:-- 4Methylindole
0.15
2.3Dimethylindole
>-
0
0.05

-05.
0
Cl)
z
0.25

0.15

0.05
a
5-Methylindole

.:;;;.-' . -.
6MethyIindoIe 7. Methylindole
o,o----..-..o

...0.05 : : : ; : :
290 320 350 380290 320 350 380290 320 350 330

EMISSION WAVELENGTH, nm
Figure 3. Emission wavelength dependence of the anisotropy of indole and methylindoles in PPG at 5O0C. Excitation
wavelengths of 267 nm (0), 277 nm (), 287 nm (s), and 297 nm (A). For the 4-methylindole, symbo' A is for
excitation at 292 nm; for 5-methylindole, symbol is for excitation at 295 nm.

wavelengths. For 5-methylindole (and, to a lesser
extent, 1-, 4-, and 7-methylindole), the anisotropy
values vary significantly with emission wavelength and
the trends depend on excitation wavelength. A
dramatic crossing pattern is seen for 5-methylindole;
between 350 and 360 nm the r value is roughly
independent of excitation wavelength, whereas at
lower (or higher) emission wavelength the r values
increase (or decrease) with increasing excitation
wavelength. The pattern observed for 5-methylindole
(and possibly the other mentioned methylindoles) can
be interpreted as arising from dual emission from the
'L and 'Li, excited stated.
3.2 Methoxyindoles: Similarly, we show the
excitation and anisotropy spectra of 4-methoxy-, 5-
methoxy-, 6-methoxy-, and 7-methoxyindole in Figure
2. Here the spectra deviate more noticeably from that
of indole. 5-Methoxyindole and 6-methoxyindole show
very red excitation spectra, whereas 4-methoxyindole
and 7-methoxyindole show relatively blue excitation
spectra. The anisotropy spectrum of each of the
methoxyindoles shows little similarity to that of indole.
A plateau is still approached on the red edge, but the
drop, between the red-edge plateau and the minimum
anisotropy region, varies within the series. For
example, 4-methoxyindole shows only a drop from r =
0.29 to r = 0.25 between 290 nm and 275 mu. 5-
Methoxyindole, on the other hand, shows r = 0.35 at
the red edge and shows a negative anisotropy at 260
nm.
The emission wavelength dependence of the
anisotropy values shows only gradual trends for all the
methoxyindoles. These trends are similar at different
excitation wavelengths and do not indicate the
existence of dual emission.
3.3 Resolution of L and Ltitnsitions:
Following the procedure of lPaleur andWeber (5), we
have analyzed the low temperature anisotropy spectra
of indoles in terms of contributions from both the 'L
and 'Li, transitions. The procedure will be described
in detail elsewhere (15). Essentially it involves
selecting values of 8,, the angle between the 'L and
1Lb transition moments, which give subspectra which
are similar to those found by Valeur and Weber for
indole. In Figures 1 and 2 these resolutions are
shown and the 8, values are given in Table I.

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 The resolutions in Figures 1-2 were made without Table I. Parameters Used to Resolve the
knowledge of' the theoretical e to be presented in the Excitation and Anisotropy Specfra of Indoles
next section. It is thus encouraging that we experi- into Component L and L, Spectra.a
mentally find relatively small (<600) values of 8 for
4-methoxy-, 6-methoxy-, and 7-methoxyindole; the
semi-empirical MO calculations predict small 8 for
Indole
Derivatives
r
(degrees)
these methoxyindoles (see below). Also, some of the
above mentioned methylindoles (1-, 4-, and 7-), for Indole 0.35 70-90 (90)
which we find poorer agreement with indole, are ones 1-Methyl- 0.35 50-70 (50)
which the MO calculations predict to have relatively 2-Methyl- 0.35 60-90 (90)
small 8bii Indole and most of the other methylindoles 3-Methyl- 0.35 60-90 (90)
4-Methyl- 0.22 60-70 (50)
(2-, 3-, 6-, and 2,3-dimethyl) show the expected 5-Methyl- 0.35 60-90 (60)
resolution with O values of approximately 6O09O0. 6-Methyl- 0.35 70-90 (90)
The 'La transition is the lowest energy transition for 7-Methyl- 0.35 50-90 (90)
these. The red edge plateau in the anisotropy spectra 2,3-Dimethyl- 0.35 60-90 (90)
is most evident for 2,3-dimethylindole and a value of Trp 0.35 60-90 (90)
0.35 is reached. For 1-, 4-, 5-, and 7-methylindole, the NATA 0.35 60-90 (90)
resolutions show the 'L and 'Li, transitions to have 4-Methoxy- 0.29 20-30 (25)
nearly the same onset (with 'Li, probably being the 5-Methoxy- 0.35 70-90 (90)
6-Methoxy- 0.35 30-40 (40)
lowest energy for 1-methylindole). 0.29 40-50 (50)
7-Methoxy-
The 'Lb transition appears to be the lowest aCofl&tjofls. in PPG at -50C. Values of in
transition for each of the methoxyindoles. The sub- parentheses were used in the resolutions shown in
spectra for 4-methoxy-, 5-methoxy-, and 7-methoxy- Figures 1-2.
indole, in Figure 2, show the fine-structured 'Li, type
sub-spectra to be to the red of the broad, featureless
La sub-spectra. Table IL Calculated Transition Dipole Moment
Directions of Indole Derivatives Using INDO/SSDCIa
and ]NDO/S-SCJ?

Indole SDCIC SCIC

4. THEORETICAL RESULTS Derivative degrees degrees
4.1. Transition Moment Directions: The most 'Li, 'L 0ba '14 'L 0ba
striking result of the calculations is the great
sensitivity of the transition moment direction to
the nature and position of substitution, and, in 2,3-dimethyl- 51.5 -41.2 87.3 36.1 -29.7 65.8
2-methyl- 42.6 -39.7 82.3 20.4 -26.6 47.0
contrast, the slight and opposite response of the L 6-methyl- 34.7 -43.9 78.6 9.2 -31.4 40.6
transition moment as shown in Table II. (The angles 5-methoxy- 49.3 -53.3 77.4 44.5 -43.8 88.3
are defined as in Figure 4.) The entries in Table II 5-methyl- 57.3 -50.9 71.8 51.6 -36.7 88.3
are arranged in order of decreasing absolute angle unsubstituted 59.2 49.9 70.9 49.4 -36.7 86.1
between the 'L and 'Li, moments. These theoretically 3-methyl- 69.4 -51.4 59.1 >3.8 -39.2 67.0
calculated values for the angle are to be compared 1-methyl- 67.9 -55.8 56.3 66.3 -42.9 >0.8
with the values determined via the above fluorescence 7-methyl- 80.1 -57.4 42.5 88.4 -41.6 50.0
anisotropy measurements (in Table I). 4-methyl- 87.8 -54.7 37.5 103.5 -40.7 35.8
6-methoxy- -8.2 -38.8 30.6 -8.8 -25.3 16.5
4-methoxy- -52.2 -62.8 10.6 130.3 -47.8 1.9
In both sets of calculations, the 1L and 1J 7-methoxy- -63.4 -67.6 4.2 106.5 -50.5 23.0
moments are predicted to be nearly parallel (8 = 0-
30) for 4-, 6-, and 7-methoxy derivatives, while 4- and
7-methyl are consistently predicted to have = 36- a) Results from -.25 singly excited and -.170 doubly excited
50. Unsubstituted indole, 5-methylindole, and 5- 1r7r* configurations and Ohno-Klopman electron
methoxyindole are consistently predicted to have the repulsion.
'Lb and 'L moments nearly perpendicular (8,, = 70- b) Results from 196 singly excited configurations and
90), and 1-methyl and 3-methylindoles are predicted Mataga-Nishimoto electron repulsion integrals.
to have intermediate values of 8 = 60-70. c) Angles are measured in degrees CCW from x which is
1.4 from the line bisecting the 5-6 bond in the direction
of atom 2. The y axis is defined by the line from atoms
4.2 Band Separations: In Table III is shown 6 to 5. (See Fig. 5).
the theoretical energy separation between the 'La and
'Lb states, ab given by INDO/S. They are
as
presented in order of increasing
calculated using correlated with those in solution if the solvent induced
the SDCI basis (column A). The pattern is quite shifts are reasonably uniform. Figure 5 shows a plot
similar for the SCI basis (column B). These numbers of the numbers in Table III vs. the separations experi-
should correlate with separations of the 'La and 'Li, mentally deduced from the anisotropy and excitation
absorption maxima in the gas phase and may be spectra.

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 Table III. Calculated LaLp Energy Differences for
Indole Derivatives.

a) Derivative Aa Bb
(cm') (cm')

2,3 dimethyl 5624 2909

3-methyl- 5717 3234

b)
yx 1-methyl-
6-methoxy-
6-methyl-
2-methyl-
(5813) est.
6235
6327
6346
3522
4320
4190
3814
7-methoxy- 6424 4305
Unsubstituted- 6584 3905
4-methoxy- 6607 3942
4-methyl- 6646 4284
7-methyl- 6710 4464
5-methyl- 6958 4680
Figure 4. Conventions for the indole structure used in 5-methoxy- 7347 5069
this paper. (a) shows the numbering system, the
definition of 8 (i = a,b) defining transition dipole a) From INDO/S-SDCI (Series A of Methods Section).
directions and the Platt-Petruska spectroscopic b) From INDO/S-SCI (Series B of Methods Section).
moments, t,, for the L, transition. (b) shows the t
for the L, transition.

5. DISCUSSION
The fluorescence excitation spectra and anisotropy E
C.)
excitation spectra of the 13 compounds in Figures 1-2
are nearly all distinct. Their similarities and 0
differences provide a rich and revealing statement
about the two electronic states comprising the ..'28O
nm absorption band of indoles. The results are -j.0
LU
largely understandable within the traditional frame-
work of two distinct Born-Oppenheimer vibronic -J0
manifolds, independent in the sense that individual LU

vibronic states of one electronic state are only weakly 0

coupled to those of the other by vibrations and .4-,
C
0
substitutent perturbations. E
4-
ci
The 1J transition apparently causes only small 0.
geometry changes and thus has a narrow envelope LU
with a dominant 0-0 band with weak progressions in
only a few Franck-Condon active modes, which in Calculated ELa _ELb iO cm1
solution are manifest as additional weak vibronic
structure to the blue of the dominant, sharp origin.
In contrast the 'La envelope is much broader with Figure 5. Comparison of the experimentally observed
little structure, especially in polar solvents. Its (via resolution of excitation and anisotropy spectra)
breadth allows its "0-0' to be close in energy to that and theoretically calculated energy differences between
of 'Li, even though its maximum is always at higher absorption maxima of the L fld L, StthS TheU
energy than that of 'Lb. The broad, slowly changing points compare vapor phase experimental data from
spectral curve of 'L allows the structured 'Li,, envelope references (8) with the present theoretical results.
to be observed even when the two bands are The points compare the present experimental results
completely overlapped. with the present SCI calculations. The A points
compare the results with the SDCI calculations. The
This independence means that solvent and following symbols identify the indoles: I = indole, 1 =
substituent perturbations can shift the entire 'La and 1-methylindole, 2= 2-methylindole, 3= 3-methyl-
'Lb envelopes relative to each other, changing the indole, 4 = 4-methylindole, 5 = 5-methylindole, 6 = 6-
order and spacing of the two origins. The substituent methylindole, 7 = 7-methylindole, 2,3 = 2,3-dimethyl-
perturbations will also change the characteristic indole, 40 = 4-methoxyindole, 50 = 5-methoxyindole, 60
transition dipole directions and lengths uniformly = 6-methoxyindole, and 70 = 7-methoxyindole.
within the respective envelopes. These parameters

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 dictate the characteristic anisotropy excitation
spectrum for a given molecule. If the above picture is
substantially true, whether the 1] or 'La is lower in
energy will determine, by Kasha's rule, which state
fluoresces predominantly. Thus, whether L or L, is
the lowest excited singlet (S,) should make a major
difference in the anisotropy spectrum.
5.1 Identity of i! For most of the spectra in
Figures 1-2 the anisotropy reaches a limiting high
value of 0.30-0.35 when exciting the red edge. This is
unequivocal evidence that the absorbing and emitting
transition dipoles are virtually parallel. In most of
these spectra the anisotropy drops to much lower
values when excitation is at shorter wavelengths,
indicating a substantial angle between at least some
of the absorbing and emitting moments. In such cases
it follows that the absorbing state for red edge
excitation j the emitting state, S,.
The sharpness of the 'Li, origin makes it
identifiable in each of the spectra and the anisotropy
excitation spectra divide neatly into two categories:
indole derivatives for which the anisotropy exhibits a
narrow minimum coincident with the L, origin, and
indole derivatives which show no change or a
maximum of anisotropy at the L, origin. The former
case we interpret, like those before us (5,19,20), as
indicating that 'L is S1. The latter case evidently
corresponds to 'Lb as B,.
By this criterion, 'Lv, is B, for all the methoxy
derivatives (and perhaps 1-methylindole). Dual
emission from the 'La and 'Li, states apparently occurs
for 5-methylindole, and may also occur for 1-, 4-, and
7-methylindole. For all other indoles studied, 'L is
evidently S,.
The 'La'L, energy gap from the MO calculations
should, in principle, provide predictive power regarding
the relative energy of the 'Li, and 'La origins. The
calculated energy differences correspond to vertical
excitation in a vacuum and should corre'ate with the
difference between the 'L and 'L,, absorption maxima
in the vapor phase. From Figure 5 it is seen that
vapor phase data, when available, correlate well with
the calculations. In the polar PPG condensed phase,
the 'La oscillators are all expected to be stabilized and
thus red shifted with respect to the 'Li, oscillators. If
there is a uniform red shift of the 'La band for all
indoles, the experimental EL -E1 energy gap values
in Figure 5 will shift downwthd133r an equal amount.
Since the red shift probably varies somewhat even
among the methylindoles, a perfect correlation should
not be expected, even if the theory were exact in the
vapor phase. Nonetheless, theory clearly points out
the extremes and correctly places 5-methylindole
relative to the other methylindoles. The theory, if
taken literally, appears to fail by inferring that 4-,
6-, and 7-methoxyindoles would have 'La as S,. How-
ever, as just noted, the theory does not consider the
solvent effect, which may be less for the methoxy-
indoles than for the methylindoles.
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5.2 Relative Transition Moment Directions:
In some cases there is a reasonably good agreement
between the experimentally evaluated 8 and the
angle between the dipoles predicted by both sets of
calculations. Looking first at the methoxyindoles in
Figure 2, one sees what is one of the most spectacular
results of this study. r is relatively high and nearly
independent of wavelength for 4-methoxyindole and 7-
methoxyindole, but shows almost the maximum
possible excursion for 5-methoxyindole. The relatively
high and nearly constant value of r for 4-methoxy-
indole is very strong evidence that the two transition
dipoles are nearly parallel. For 7-methoxyindole,
whose excitation spectrum is very similar, the drop in
r is also small, whereas the drop in r for 6-methoxy-
indole is about half the large drop seen for 5-methoxy-
indole. From Table II it is seen that this pattern is
robustly predicted by semi-empirical MO calculations.
This occurs mainly because the 'Li, transition moment
direction is particularly sensitive to the position of
substitution whereas the 'L direction is only weakly
affected and in the opposite sense. With either
parameter set employed in our calculations, quite
small values of are predicted for 4-, 6-, and 7-
methoxyindole, while a large value is predicted for
5-methoxyindole. These observations affirm the
benzenoid character of the indole 'Li, transition, which
has been asserted previously on theoretical grounds
(7,21,22). Elsewhere we will further discuss the
INDO/S results and compare these with predictions of
the Platt-Petruska theory (23,24).
Regarding methyl substitution, 2-methylindole, 3-
methylindole and 2,3-dimethylindole have 'La bands
which are the most red shifted, presumably becanse
the 'La transition has a large component in the 2-3
double bond. This is especially true for 2,3-
dimethylindole, which has a pronounced broadening
and by far the longest high anisotropy plateau at the
red edge.
The remaining methylindoles fall into an
intermediate class characterized by having their 'La
and 'Li, origins nearly degenerate. This is particularly
evident for 5-methylindole, for which the emission-
wavelength dependent r values, low red edge
excitation r values, and shallow excitation r spectrum,
strongly indicate that emission occurs from both the
'La and 'Li, states. Dual emission from indoles in rigid
solution has been previously reported (19,25,26) and
it is reasonable to expect cases where the 'La and 'Li,
origins are within kT of one another.) The near
degeneracy of the 'La and 'Li, origins thus leads to an
explanation of the unusual anisotropy patterns for 5-
methylindole and the other methyl derivations of the
benzoid ring (i.e., the red edge excitation r values for
these methylindoles are lower than 0.30-0.35 due to
dual emission). The INDO calculations also predict
4-, 5-, and 7-methylindole to have E,-ELb gaps that
are intermediate (see Figure 5) between the dominant
'Lafluorescing chromophores (e.g., 2,3-dimethyl-, 2-,
and 3-methyl-) and the dominant 'Lb-fluorescing
chromophores (e.g., 5-methoxyindole).
 6. CONCLUSIONS
For the most part this study affirms the often used
picture of two independent, over-lapping transitions for
the properties of the 280 nm absorption band for all
methylindoles and the four methoxyindoles substituted
on the benzene ring. The methoxyindoles exhibit a
fluorescence anisotropy consistent with having 'Li, as
the lowest excited singlet state in cold PPG, whereas
methyl derivatives of indole's 5-membered ring have
'L lowest (predominantly). Methyl derivatives of
indole's benzoid ring show an intermediate photo-
physical pattern. In particular, 5-methylindole
exhibits dual emission from its 'La and 'Li, states.
The experimental observation that 4-, 6- and 7-
methoxyindole have the 'La and 'Lb transition dipoles
substantially parallel is consistent with MO theory,
which asserts that the 'Lb moment makes wide swings
in a direction depending upon the substitution site
because of the benzenoid nature of this state. The 'La
moment direction is theoretically seen to be far less
sensitive to substitution at least partly because about
half the intensity comes from an ethylene-like
transition in the 2-3 double bond.
7. ACKNOWLEDGEMENTS
This research was supported by National Science
Foundation grant DMB 88-06113 to MRE and National
Institutes of Health grant GM 31824 to PRC.
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