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ABSORPTION SPECTRA OF

AND

FLUORESCENCE DYES

RHODAMINE

I.

A.

Gofman

UDC 535.34./37

On c o m p a r i n g the absorption and f l u o r e s c e n c e s p e c t r a of solutions of a s e r i e s of rhodamine dyes [1-5]* of the g e n e r a l formula R1HNN~NI~O\'d~//NHR~',,,,//,I "9 ~ / / ' , , / /
/N--COOH

with different substituents at the rhodamine amino n i t r o g e n s it is immedia.tely evident that a.I1 of the studied compounds can be divided into two groups [6]. The compounds of one group show a c h a r a c t e r i s t i c m i r r o r image s y m m e t r y of the absorption and f l u o r e s e e n c e s p e e t r a . The half-w~dth of the s p e c t r a of t h e s e e o m pounds lies within the l i m i t s of 1200-1500 cm -1. Compounds of the second group, as is evident f r o m Fig. 1, a r e e h a r a e t e N z e d by b r o a d e r absorption and f l u o r e s e e n e e s p e c t r a and in the m a j o r i t y of e a s e s a m i r r o r i m a g e s y m m e t r y between the absorption and f l u o r e s e e n c e s p e c t r a is absent. *The author t a k e s t h i s opportunity to e x p r e s s his gratitude to P r o f e s s o r I. S. Ioffe f o r kindly making the r h o d a m i n e dyes a v a i l a b l e .

W~xg~) , ~

lO c -

I" / / \

Fig. 1. Absorption and f l u o r e s c e n c e s p e c t r a of solutions of rhodamine d e r i v a t i v e s in ethanol. The c o m pounds a r e : a) unsubstituted r h o d a mine; b) rhodol; c) N, N ' - d i - a - a l a n y l rhodam ine; d) N - p h e n y l - N ' -fi -p.henyl ethylrhodamine; e) N , N ' - d i p y r i midylrhodamine; f) N, N' - d i - a - p y r i dylrhodamine.

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z2,8

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T r a n s l a t e d f r o m Zhurnal Prikladnoi Spektroskopii, Vol. 17, No. 6, pp. 1115-1118, D e c e m b e r , 1972. Original a r t i c l e submitted June 8, 1971; revision submitted June 23, 1972.
}974 Consultants Bureau, a division of Plenum Publishing Corporation, 227 Test I7th Street, New York, N. Y. 10011. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission of the publisher. A copy of this article is available from the publisher for $15.00.

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A s i m i l a r phenomenon h a s been o b s e r v e d p r e v i o u s l y in the a n a l y s i s of the a b s o r p t i o n and f l u o r e s c e n c e s p e c t r a of p h t h a l i m i d e d e r i v a t i v e s [7-10]. In a g r e e m e n t with the t e r Substance Kabs, 9l0 s KfJuor minology suggested in [7-10], the s p e c t r a of r h o d a m i n e d y e s , 9 lOs which a r e c h a r a c t e r i z e d by m i r r o r i m a g e s y m m e t r y between the a b s o r p t i o n and f l u o r e s c e n c e s p e c t r a , can be d e s i g n a t e d N, N'di-ce-pyridlyrhod6,4 6,5 m o d u l a t i o n s p e c t r a . The s p e c t r a of the compounds which do amine N, N'- dipyrimidylrhod4,8 4,7 not p o s s e s s m i r r o r i m a g e s y m m e t r y , a p p a r e n t l y , a r e d e s amine ignated extinction s p e c t r a . As shown in o t h e r s t u d i e s [7-10], N, N'di-a- alanylrhod5,4 5,5 the dependence Av = Kv2c is c h a r a c t e r i s t i c f o r extinction s p e c amine t r a where Av i s the s p e c t r u m halfwidth; v c is a frequency 5.1 4,9 N-phenyl-N-B-phenyl- . _ethylrhodamine a p p r o x i m a t e l y coinciding with Vmax, and K i s a constant, N-phenyl-N'-benzykohod 5,5 5,5 having the s a m e value for both the a b s o r p t i o n s p e c t r a and the amine f l u o r e s c e n c e s p e c t r a of the given s u b s t a n c e . In the p r e s e n t w o r k v a l u e s of the constant K w e r e c a l c u l a t e d f o r d e r i v a t i v e s o f r h o d a m i n e , the s p e c t r a of which did not p o s s e s s m i r r o r i m a g e s y m m e t r y in the f r e q u e n c y s c a l e . As seen f r o m Table 1, f o r all the studied compounds the v a l u e s of the constant K, obtained on the b a s i s of the a b s o r p tion and f l u o r e s c e n c e s p e c t r a w e r e p r a c t i c a l l y c o i n c i d e n t . It was of i n t e r e s t to s e e what was the explanation f o r the t r a n s i t i o n f r o m modulation s p e c t r a to e x t i n c t i o n s p e c t r a in the c a s e of r h o d a m i n e d y e s . In p r e v i o u s studies [7-10] it was noted that t h i s t r a n s i t i o n could be due to a d i s t u r b a n c e of the s y m m e t r y of the e l e c t r o n cloud in the m o l e c u l e u n d e r the influence of the s u b s t i t u e n t g r o u p s . During study of the s p e c t r a of the p h t h a l i m i d e s it was noted [11] that t r a n s i t i o n f r o m m o d u l a t i o n s p e c t r a to extinction s p e c t r a o c c u r r e d in line with b a t h o c h r o m i c shift of the s p e c t r a . In addition to t h i s it h a s been pointed out [7] that the c h a r a c t e r of s p e c t r a of complex m o l e c u l e s can be due not only to the s y m m e t r y of the e l e c t r o n cloud but a l s o to o s c i l l a t i o n of the c h a r g e between the n u c l e i . Among the d e r i v a t i v e s of r h o d a m i n e which p o s s e s s extinction s p e c t r a a r e compounds, the m o l e c u l e s of which a r e m o r e o r l e s s s y m m e t r i c a l . In addition to d e r i v a t i v e s of r h o d a m i n e which contain different a u x o c h r o m e g r o u p s , extinction s p e c t r a a r e a l s o p o s s e s s e d by a n u m b e r of compounds which contain the s a m e a u x o c h r o m e g r o u p s . Strong light a b s o r p t i o n by dyes is u s u a l l y linked with o s c i l l a t i o n of the c h a r g e between the a u x o c h r o m e groups when light quantum i s a b s o r b e d . It can be a s s u m e d that in the c a s e of r h o d a m i n e dyes the t r a n s i t i o n f r o m modulation s p e c t r a i s due to a d e c r e a s e in the e a s e of o s c i l l a t i o n of the ~ - e l e c t r o n cloud b e t w e e n t h e a u x o c h r o m e g r o u p s . In o r d e r to v e r i f y t h i s a s s u m p t i o n the a b s o r p t i o n and f l u o r e s c e n c e s p e c t r a w e r e c o m p a r e d of unsubstituted r h o d a m i n e (both a u x o c h r o m e g r o u p s NH2), rhodol (one group NH 2 the o t h e r OH) and d i - ~ - a l a n y l r h o d a m i n e (R i = R 2 = CH2COOH ) . If one s t a r t s f r o m ideas c o n c e r n i n g the s y m m e t r y of the e l e c t r o n cloud in the indicated m o l e c u l e s , then it might be expected that unsubstituted r h o d a m i n e and d i - a - a l a n y l r h o d a m i n e would p o s s e s s s i m i l a r modulation s p e c t r a , w h e r e a s rhodol, the m o l e cule of which contains d i f f e r e n t a u x o c h r o m e g r o u p s , should have a s p e c t r u m c o n s i d e r a b l y d i f f e r e n t f r o m the s p e c t r u m of u n s u b s t i t u t e d r h o d a m i n e . H o w e v e r it was. found that u n s u b s t i t u t e d r h o d a m i n e and rhodol p o s s e s s e d m i r r o r - i m a g e s y m m e t r i c a l f l u o r e s c e n c e and a b s o r p t i o n s p e c t r a (for unsubstituted r h o d a m i n e and rhodol Auabs = Aufluor = 1200 and 1600 cm -i) w h e r e a s d i - o - a l a n y l r h o d a m i n e was c h a r a c t e r i z e d by an extinction s p e c t r u m (Avabs = 2100 cm - l , Aufluor = 1900 cm - i , Kab s = 5 . 4 . 1 0 -G, Kfluo r = 5.5 -10-6). Although in the rhodol m o l e c u l e the e l e c t r o n cloud m u s t be somewhat d i s p l a c e d t o w a r d s the hydroxyl g r o u p , n e v e r t h e l e s s o s c i l l a t i o n of the c h a r g e , when a light quantum i s a b s o r b e d , o c c u r s r a t h e r e a s i l y [12]. E s s e n t i a l l y rhodol h a s the n a r r o w a b s o r p t i o n and f l u o r e s c e n c e s p e c t r a t y p i c a l for dyes p o s s e s s i n g m i r r o r i m a g e s y m m e t r y . In the c a s e of d i - ~ - a l a n y l r h o d a m i n e o s c i l l a t i o n of the c h a r g e between the a u x o c h r o m e g r o u p s m a y be h i n d e r e d , since the p r e s e n c e of a c c e p t o r c a r b o x y l g r o u p s in the substituent at the amino n i t r o g e n s of the r h o d a m i n e should c a u s e a d r a w i n g off of the e l e c t r o n s of the u n s h a r e d p a i r s of the n i t r o g e n a t o m s t o w a r d s t h e s e g r o u p s . This fact a p p a r e n t l y i s a l s o the r e a s o n that d i - a - a l a n y l r h o d a m i n e p o s s e s s e s extinction s p e c t r a . 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 i s c h a r a c t e r i s t i c f o r r h o d a m i n e d y e s [13], the likelihood of it o c c u r ring i n c r e a s e s in the c a s e w h e r e the s u b s t i t u e n t eontains a r o m a t i c r i n g s d i r e c t l y linked with the amino n i t rogen a t o m s of the r h o d a m i n e . At the s a m e t i m e t h e s e compounds p o s s e s s extinction s p e c t r a . When a light quantum i s a b s o r b e d by m o l e c u l e s of t h e s e compounds a p p a r e n t l y t h e r e a r e two c o m p e t i n g p r o c e s s e s - o s c i l l a t i o n of the c h a r g e between the a u x o c h r o m e g r o u p s and 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 f r o m the donor to the a c c e p t o r g r o u p . The e l e c t r o n s of the u n s h a r e d p a i r s of the n i t r o g e n a t o m s p a r t i c i p a t e in both

TABLE 1. Values of the K C o n s t a n t s f o r Some D e r i v a t i v e s of Rhodamine

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p r o c e s s e s . T h e r e f o r e an i n c r e a s e in the probability of i n t r a m o l e c u l a r charge t r a n s f e r entails a d e c r e a s e in the probability of oscillation of the charge between the a u x o c h r o m e groups. This is indicated by a d e c r e a s e in intensity of the longwave absorption band with i n c r e a s e in the intensity of the band c o r r e s p o n d i n g to intram01ecular charge t r a n s f e r [13]. By using the formula [14] q2 = 0.3.105 f e / ~ ~2, it is possible to evaluate the amplitude of the o s c i l l a tion of the electron cloud qe when a light quantum is absorbed. In the formula fe is the o s c i l l a t o r strength and v is the mean frequency of the electron transition c o r r e s p o n d i n g to the longwave absorption band. F r o m a s i m i l a r formula [15], knowing the o s c i l l a t o r strength fIaCT for the band 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 charge t r a n s f e r , it is possible to evaluate the charge displacement qIaCT for the charge t r a n s f e r p r o c e s s in the molecule from donor to a c c e p t o r group. It was found that in compounds for which modulation s p e c t r a are c h a r a c t e r i s t i c , the value of the charge displacement for i n t r a m o t e c u l a r charge t r a n s f e r is 2 to 3 t i m e s l e s s than the amplitude of oscillation of the ~-electron cloud. W h e r e a s in compounds p o s s e s s i n g extinction s p e c t r a the charge displacement for i n t r a m o l e c u l a r charge t r a n s f e r equals or is even g r e a t e r than the o s c i l lation amplitude of the c h a r g e s between the auxochrome g r o u p s . The given data show tha~ :in the case of rhodamine dyes besides s y m m e t r y of the electron cloud, the probability of oscillation of charge between the auxochrome groups, which in turn is closely linked with the probability of i n t r a m o l e c u l a r charge t r a n s f e r , exerts a considerable influence on the c h a r a c t e r of the a b sorption and f l u o r e s c e n c e s p e c t r a .
LITERATURE CITED

1. 2. 3. 4. 5.

I.S. I.S. I.S. I.S. I.S.

Ioffe Ioffe Ioge Ioffe Ioffe

and and and and and

V. V. M. N. N.

F. F. Z. A. A.

Otten, Zh. Obshch. Khim., 3_1, 1511 (1961). Often, Zh. Obshch. Khim., 3_.~2, 1196 (1962). Zal'manovich, Zh. Obshch. Khim., 3_22, 1480 (1962). Selezneva, Zh, Obshch. Khim., 3__22,1485 (1962). Selezneva, Zh. Obshch. Kh[m., 3_4, 2041 (1964).

6. 7. 8. 9. 10. 11. 12. 13. 14. 15.

E . N . Viktorova and I. A. Gofman, Zh. Fiz. Khim., 3 _ ~ 4 , 2643 (1965). B . S . Neporent, Zh. l~ksperim, i. Teor. Fiz., 21, 172 (1951). P . P . Feofilovand I. G. Fraerman, Dokl. Akad. Nauk, SSSR, 8 _ ~ 7 , 931 (1952). B . S . Neporent, V. V. Zelinskii, and V. P. Klochkov, Dokl. Akad. Nauk SSSR, 92, 927 (1953). ]3. S. Neporent, Zh. Fiz. Khim., 3 _ _ 0 0 , 1048 (1956). V . P . Klochkov, Zh. Fiz. Khim., 2 _ _ 9 9 , 1432 (1955). V . F . Otten, Thesis, Leningrad (1963). I . A . Gofman, Zh. Prikl. Spektroskopii, 1 _ ~ 2 , 1067 (1970). A . N . Terenin, Photonics of Dye Molecules [in Russian], Nauka, Leningrad (1967). W. Kauzman, Introduction to Quantum Chemistry, Academic Press (1957).

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