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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 .
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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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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
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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
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V. V. M. N. N.
F. F. Z. A. A.
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