EFFECT OF INTRAMOLECULAR CHARGE TRANSFER

ON E L E C T R O N I C SPECTRA AND FLUORESCENCE

OF RHODAMINE DYES

I. A. Gofman UDC 535.37:541.6

I n t r a m o l e c u l a r c h a r g e t r a n s f e r has a significant effect on the s p e c t r a l and f l u o r e s c e n t c h a r a c t e r i s t i c s

of organic m o l e c u l e s - it c a u s e s a shift in the a b s o r p t i o n and f l u o r e s c e n c e bands and changes in the quan-
tum yields of f l u o r e s c e n c e . The a i m of the p r e s e n t work was to investigate the relationship between i n t r a -
m o l e c u l a r c h a r g e t r a n s f e r and the donor p r o p e r t i e s of the substituents in the molecule, and the effect of
the c h a r g e - t r a n s f e r state on the s p e c t r a l and f l u o r e s c e n t c h a r a c t e r i s t i c s of organic m o l e c u l e s .
Rhodamine dyes with m o l e c u l e s containing both an e l e c t r o n donor (amino group) and e l e c t r o n a c c e p t o r
(carboxyl group) as substituents can give c o n s i d e r a b l e i n f o r m a t i o n about the effect of the c h a r g e - t r a n s f e r
s t a t e on the a b s o r p t i o n s p e c t r a and f l u o r e s c e n c e of m o l e c u l e s . As T a n a k a and Nagakura [1] showed, m o l e -
cules of such type should be c h a r a c t e r i z e d by a t r a n s i t i o n with e n e r g y 4-4.5 eV, c o r r e s p o n d i n g to i n t r a -
m o l e c u l a r c h a r g e t r a n s f e r . In the p r e s e n t work we used a S F - 4 s p e c t r o p h o t o m e t e r to obtain the absorption
s p e c t r a of s e v e r a l rhodamine dyes of the type
RI ~ Rx
\~" 0 /

R,/N\/\ii/~i'~N'R,

(Rx=R~=H, \/N~//\// RI=R~=C~Hs,

RI=H, R~=C2H~, RI=R2=C4H9,
RI=H, R~=C~H~, /i -Coo- RI=H, R~=CoHn, I
RI=H, R~=CH2--CH~--C6Hs, RI=H, Rz=CeH~,
RI=H, R~=CH~--C6Hs, \/ R1=H , RI=C6H4--CH,)
and +
R3\ .-------~ , R~
~N, 0 N/
R/ "/\/\(\~ \R~

\/\//\//
I

R~=CsHs, R~=CsHs, 1I
R,=CH~--CeHs, R4=CH2--CHz--C6H6)"
\/
The s p e c t r a of all the investigated compounds showed a band in the region 33,000-34,000 cm -1 (energy 4.20-
4.27 eV). T h i s band can be attributed to i n t r a m o l e c u l a r c h a r g e t r a n s f e r (ICT). In this e a s e the m o l a r ab-
s o r p t i o n coefficient of this band ( q C T ) in the different rhodamine d e r i v a t i v e s will depend on the ionization
potential of the e l e c t r o n - d o n o r group. Such a relationship is shown in Fig. 1. The ionization potentials
for the NH2, NHC2H5, N(C2Hs)2, and NHC6H 5 groups a r e taken f r o m the l i t e r a t u r e [2]. As Fig. 1 shows, the
r e l a t i o n s h i p between q C T and the ionization potential I is c l e a r l y l i n e a r . T h i s g r a p h could be used to de-
t e r m i n e the ionization potentials of substituents for which t h e r e a r e no published data.
The a b s o r p t i o n band in the visible region of the s p e c t r u m can be r e g a r d e d as the r e s u l t of i n t e r a c t i o n
of the i n t r a m o l e e u l a r c h a r g e - t r a n s f e r s t a t e with the state L~. In this case, as in the c a s e of c o m p l e x e s

T r a n s l a t e d f r o m Zhurnal P r i k l a d n o i Spektroskopii, Vol. 12, No. 6, pp. 1067-1070, June, 1970.

Original a r t i c l e submitted June 26, 1969.

9 I97j Consultants Bureau, a division of Plenum Publishing Corporation, 227 West 17th Street, New York,
N. Y. 10011. All rights reserved. This article cannot be reproduced for any purpose whatsoever without
permission of the publisher. A copy of this article is available from the publisher for $15.00.

798
 max
'Y abs. e.tO "4

9 i0 -4
IC

ol
6 fgOOO ro

]
4

f&OOO
8, 9 Io 11 I , e g ? 8 9 I0 l't I, eVI2

Fig. 1 Fig. 2
Fig. 1o Plot of elC T against ionization potential of donor group of rho-
damine d e r i v a t i v e s .
Fig. 2. P l o t s of positio n of long-wave absorption band (1) and e of
long-wave absorption band (2) against ionization potential of donor group
of rhodamine derivatives.

with i n t e r m o l e c u l a r c h a r g e t r a n s f e r , there will be a definite relationship between vmax

abs of the long-wave
band and the ionization potential of the substituent. Such a relationship is shown in Fig. 2.
Reduction of the ionization potential of the substituent leads to an i n c r e a s e in the intensity of the ICT
band (Fig. 1) and a reduction of the intensity of the long-wave band (Fig. 2). This change in intensity of
the bands c o r r e s p o n d s with the proposed s c h e m e [3, 4] of redistribution of intensity between the bands.
A c c o r d i n g to this scheme, an enhancement of the r o l e of the c h a r g e - t r a n s f e r state will also lead to an in-
c r e a s e in the probability of a d i r e c t transition of the molecule f r o m the ground state to the lower triplet
state. In the p r e s e n t work we investigated the absorption s p e c t r a of alcoholic solutions of some rhodamine
dyes in a 50-ram thick l a y e r and found weak bands with e ~ 102 in the region 13,000-14,000 cm -1. T h e s e
low-intensity bands can be a s c r i b e d either to a n ~ rr*, or a singtet-triplet, transition. The existence of
the n ~ rr* band in the f a r red region in a p o l a r solvent is unlikely, and hence it can be a s s u m e d that this
band is due to a d i r e c t transition f r o m the singlet to the lower triplet state, amplified by the effect of the
c h a r g e - t r a n s f e r state.
The existence of i n t r a m o l e c u l a r c h a r g e t r a n s f e r affects the quantum yields of f l u o r e s c e n c e . It was
shown in [5] that the investigated rhodamine dyes can be divided into two g r o u p s . Compounds of one group
a r e c h a r a c t e r i z e d by a c o r r e l a t i o n between the quantum yield of f l u o r e s c e n c e B~u and the lifetime of the
excited state r . In these compounds quenching o c c u r s in the excited state, ano the main quenching m e c h -
a n i s m appears to be d i r e c t c o n v e r s i o n f r o m the excited state to the ground state. Other rhodamine dyes
show no c o r r e l a t i o n between Bqp and r. In the case of these compounds there is a c o r r e l a t i o n between
B~lU and eICT (Fig. 3). The quantum yield of fluorescence, the lifetime of the excited state, and the natural
lifetime rnat a r e connected by the relationship
qu
Bfl S
' ~ - - - - mat
where S is the fraction of absorbed quanta which are not quenched by type I quenching, i.e., the fraction of
quanta causing electronic excitation [6]. In the p r e s e n t work we calculated the values of m a t , the ratios
B q l / r , and the values of S for s e v e r a l rhodamine dyes. F o r all group I compounds the ratio B~lU/r was
a p p r o x i m a t e l y the same, and S was close to unity, i.e., in these compounds quenching o c c u r s in the excited
state. The values of q C T for these compounds a r e v e r y close together and lie in the range 2-2.5 9104. In
group II compounds the ratio t3plU/7 is no longer constant, and S is less than unity, i.e., type II quenching

799
 s
qu 1.0

M
t o~
ta

tr
O2
0.5

O 9

, , , , , , m

e ,~ e ~ICT ' -I0"~ 2 6 SlCT .I0 -4

Fig. 3 Fig. 4
Fig. 3. Plot of absolute quantum yields of f l u o r e s c e n c e against
eICT for group II rhodamine d e r i v a t i v e s .
Fig. 4. Plot of S against eICT f o r rhodamine d e r i v a t i v e s .

begins to play an a p p r e c i a b l e r o l e . In this c a s e t h e r e is a c o r r e l a t i o n between the i n c r e a s e in eICT and

reduction of the value of S (Fig. 4). The r e s u l t of e n h a n c e m e n t of the role of the c h a r g e - t r a n s f e r state is
that the r e d i s t r i b u t i o n of e l e c t r o n density in the molecule due to i n t r a m o l e c u l a r c h a r g e t r a n s f e r c o m p e t e s
with excitation of the ~r e l e c t r o n s of the molecule, which leads to a reduction of the quantum yield of fluo-
r e s c e n c e and to f a i l u r e of the c o r r e l a t i o n between the values of Bfqu_ and the lifetime of the excited state.
The e x i s t e n c e of the c h a r g e - t r a n s f e r state g r e a t l y f a c i l i t a t e s the t r a n s i t i o n of the molecule to the triplet
s t a t e [7]. Hence, in rhodamine d e r i v a t i v e s in which i n t r a m o l e c u l a r c h a r g e - t r a n s f e r is m o s t pronounced
the quenching in the excited state m a y be effected either by d i r e c t c o n v e r s i o n f r o m the excited state to the
ground state, or by a nonradiative t r a n s i t i o n to the t r i p l e t state.

LITERATURE CITED

I. J. T a n a k a and S. Nagakura, J. C h e m . Phys., 24, 311 (1956).

2. F. A. Matsen, J. A m . C h e m . Soc., 72, 5243 (1950).
3. J. N. Murrell, Mol. Phys., 3, 319 (1960).
4. H. T s u b o m u r a and R. S. Muihken, J. A m . Chem. Soc., 82, 5966 (1960).
5. E. N. Viktorova and I. A. Gofman, Zh. Fiz. Khim., 39, 2643 (1965).
6. N. A. B o r i s e v i c h , Excitated States of Complex Molecules in the Gas P h a s e [in Russian], Nauka i
Tekhnika, Minsk (1967).
784 S. P. McGlynn, C h e m . Rev., 58, 1113 (1958).

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