METZGER, et al.
3554 densed phase products providing support for two theories of decomposition mechanisms. 3. Sma!l quantities of NH4were found, but no Clod. NH4+leaving the condensed phase was detected with the electron beam turncd off. Clod-, on the other hand, could o n l y have been detected by the loss of two electrons. C104 ~ o u l dhave been formed, but unimolccularly decomposed so rapidly as not to be detected. 4. No evidence for Clz was found. Atomic chlorine was formed among sll decomposition. species. This is probably due to the low pressure studied. This checks
with the results of Guillory and King, but is a t variance with the results of a number of other investigators. 5. Nitrogen, NzO, NOz, and HOC1 were riot detectable as condensed phase decomposition products. 6. There is evidence that the majority of all proposed reactions of AP decomposition take place ih the condensed phase at least to some extent. Thus, sufficient exothermic reactions can bc made available under proper pressure conditions to feed energy to the prime condensed phase endothermic reactions and to sustain combustion once the reaction chain is established.
et on the Fading Rate of Photochromic 3-Substituted
Benzothiazolinic Spiropyrans by A. Samat, J. Metzger,* Laborntoire de chimie organique A associe’ au C.N.R.S. (LA126), Universiti de Provence, 1S-Marseille (ZSO), France
F. Mentienne, F. Garnier, J. E. Dubois, Laoortztoire de chimie organique physique associe’ au C.N.R.S. (LASd), UniversitB de Paris V U , 75-Paris (Se), France
and R.Guglielmetti Laborntoire de synthhse organique, Universitd de Bretagne Occidentale, 29283 Brest-Ceder, France (Reeeiised March SO, 1972) Publication costs assisted by the Universite‘ de Rretagne Occidentale
Reversible transformations of spiropyrans into merocyanines are studied in a series of seventeen photochromic 3-substituted benzothiazolinic spiropyrans. The absorption spectra of the colored photomerocyanines and their first-order tjhermal fading kinetics are followed using a rapid scanning spectrometer coupled to a flash photolysis apparatus. Activation energies and entropies are calculated in toluene. The rate processes are shown to be very sensitive to 1-1bonding of the solvent and to the nature and position of substituents; a rate enhancement of lo5is observed between the substituents X = OCH3and X = i-C3H7. The data indicate that steric hindrance of substituents in the 3 position of a planar photomerocyanine has major importance in the rate of corwersion of the colored form back to the spiropyran.
Introduction Spiropyrans arc known to behave as photochromic compounds giving merocyanirie dyes when uv irradiated. The stabi1i.y of the photomerocyanine is related to the high degree of conjugation allowed by a nearly planar conformation. A great deal of data collected on the spiropyrans ha9 led to the structure and properties of this colorltm form S. On the other hand, thermodynamic and spectroscopic properties of the colored form and the cffeet of substituent X in the 3 position are not very ne11 known. In the work reported here, we arialyzc thc problem, oftcn mentioned in the literature but rarely discussed, of the conformation and stability T h e Journal of Physical Chemistry, Vol. 7 6 , N o . $4, 197.9
5’
0 NO,
dZ’O s
+&;@16
CHJ
hduv)
~===.=2
7
OCH,
S
CH:,
M
B'EKZOTHIAZOLINIC SPIROPYRANS
PHOTOCHRORIIC 3-SUHETITUTED
3555
-Table I : Kinetic, Thermodynamic, and Spectral Data of 3-Substituted Benzothiazoliriic Spiropyrans
Compound
k, sec-1, at 25'
--Toluene-----------------------A H + , koa1 mol -1 E,, kcal mol-'
~-Ethanol-----
nm (visible)
Amax,
AS*,
eu
2.5
21.7 i 0 . 3
21.1 =t0 . 3
1 7 . 1 f 0.2
23.2
k , sec-1, a t 26'
BT2 BT3
680b
21.8 I 0 . 4 20.1 i 0 . 5
21.2 1 0 . 4 19.5 =k 0 . 5
18.8 I 0 . 3 19.5 f 0.5
BT4
612
18.9 i 0 . 2
18.3 I 0.2
18.8 i 0 . 2
25.6 f 0.5
25.0 i 0.5
16.3 Ifi 0 . 2
600, (545), 7 , 7 X 420 635, 410 15.5 x 10-4 610, 5.7 x !0-3 420-410 620, 4.65 X 610-590, 400 640, 420 (7 X 1 P ) "
24.1 i 0 . 2
23.5 rt: 0 . 2
12.3 f 0 . 2
625, 415
BT 1
BT5 BT6
9.5
x
10-3
16.2 X
Lax, nm (visible)
490, 420
542
412.5 430
430
532(415)
BT7
76
19.3 i 0 . 7
18.7 i 0.7
12.8 i 0.5
635, 415
5.85 X
BT8
163
17.4 i 0 . 2
16.8 f 0 . 2
7 . 4 i 0. I
1.68 X 10-1 529 (407)
BT9
17.5
19.3 i 0 . 7
18.7 I 0.7
10.3 f 0.7
605, 425, 400 605
BTlO
18
18.9 I 0 . 3
18.3 i 0 . 3
8.7 i0.2
605, 405
596 (402)
2.07 X lo-* 532(404) 21.8 X lo-*
532(402)
BTll
9.9
20.1 I 0 . 3
19.5 i 0 . 3
11.7 I 0 . 2
610, 400
8.8 X
530(408)
BT12
6.44
21.2 i: 0.2
20.6 i 0 . 2
14.8 i 0 . 2
635, 395
12.5 X
530(408)
BT13
5.25
20.0 f 0 . 3
18.4 i 0 . 3
10.1 f 0.2
620, 405
3.86 X
620(398)
BT14
4.74
19.5 i 0 . 2
18.9 i 0 . 2
8.1 i 0.2
620, 405
2.34 X
525(402)
BTl5
3.13
21.9
0.5
21.3 I 0 . 5
15.2 4 0 . 4
605, 395
6.2,i X lo-'
530(408)
BT16
3.04
19.4 f 0.2
18.8 f 0 . 2
7.3 i0.2
19.8i0.2
19.2i0.1
11.2f0.1
BTl7
10.8
* Bynthetizetl and studied by R. Guglielmetti16 (for comparison).
-~-------
of a photomerccyanine in relation to substituents in the
3 position.1--" We have determined in two solvents and at different temperatures the rate constants of the thermal decoloration reaction and the absorption spectra of a series of pho~ochromic~-~ 3-substituted benzothiazolinic spiropyrans syrithetized in the Department of Organic Chemistry in the University of Provence.lo~l1
~ x ~ ~ r i ~Section e n t ~ l A Aash photolysis apparatus available in the Physical Organic Chemistry Laboratory at Paris was used to induce the opcriing of the Cn-O1 bond of the colorless form and to moduee the colored photomerocyanine uerivative. The visible absorption spectrum of this open form w-aci recorded on a scanning Warner-Swasey spcctrometer 11 hie11 was coupled with the flash photolysis apparatus and was operated a t high speed (1 spectrum per millisecond). The spectrometer was
'IC, sec-I, a t 25.4'.
620 650,440, 425
527 1 0 . 0 5 X 1 0 - 4 520
Approximate value.
programmed to allow the rccording of several successive spectra. Prom these spectra we measured the kinetics (1) M. W.Windsor, I t . S.Moore, and J. It. Novack, Spectrochim. Acta, 18, 1364 (1962). (2) J. Ch. Metras, M. Mosse, and C. Wippler, J . Chim. Phys., 62, 659 (1965). (3) T. Bercovici, R. Heiligman-Rim, and E. Fischer, Mol. Photochem., 1 , 2 3 (1969). (4) R. Heiligman-Kim, Y. Hirshberg, and E. Fischer, J . P h p . Chem., 66,2465,2470 (1962). (5) Y . Ilirshberg and E. Fischer, J . Chem. Soc., 3129 (1954). (6) J. Arnaud, M. Kiclause, and C. Wippler, J . Chim. Phys., 69, 2150 (1968). (7) R. Guglielmetti and J. Metzger, Bull. SOC.Chim. Fr., 2824 (1967). (8) R. Guglielmetti, E. Daviii, arid J. Metzger, i h i d , , 556 (1971). (9) J. ltondon, R. Guglielmetti, and J. Metsger, ibid., 3029 (1971). (10) R. Guglielnietti and J. Metzger, ibid., 3029 (1969). (11) A. Saniat, Organic Chemistry Speciality Thesis, Marseilles, 1972.
The Journal of Physical Chemistry, VoE. 7 0 , S o . 24,1972
Figure 1. Effect of spiropyran BT5 concentration 011 the precipitation of the colored open form a t different temperatures in toluene.
of disappearance of the colored form 1\I and calculated the kinetic constants of ring closure (/ea). Cells of path 10 cm were uscd. For kinetic measurements the temperature 7f cells was controlled (+0.1") by the circulation of water from an external thermostat. Two flash lamps produced a discharge with an energy of about SO0 .I in a few microseconds. The compounds investigated are represented by the main formula S with X = CH3, C2H5, i-CaH7, cyclohexyl, Ocl-&, 0 6 g N 6 , SC&, ~ C I $ & CGH4Br, , CeH4C1, CeB4F7 CJ34CH3, CgI%OcH3, CGH~OH,anaphthyl, &naphthyl The absorption spectra and fading rates were determined in ethanol (H20= 200 ppm) at 26" and in toluene (HzO =- 20 ppm) a t 15, 2 5 , 3 5 , 4 5 , and 55". These results were used to calculate the activation enthalpies and entropies in the last solvent (Table I). The concentration ranges were about 10-5 to mol/l. owing to complex phenomena which appeared a t high concentrations (lo+ to 1W3mol,/l.) with some compounds (X = OCHS, OC&, 8CR3, SCeH5), Thus with the compound X = OCll,, the open form precipitates in toluene at A conocntration level which is a function of temperature ELR shown in Figure 1. The synthesis of the spiropyran with a phenoxy group in the S position leads to a colored product containing a great proportion of the photomerocyanine derivative. We thermally fncfed the solution in order to obtain the spiropyranic forni of the compound. The 3-substituted spiropyransr with cihloro and hydroxy functional groups are obtained partly as open form but they degrade when flashed.
c&,
Results and Discussion TWOimportant features appear in Table I. The first is a high sensitivity of the ring closure rate to thc solvent, arid the second is an important structure The Journal
0.f
Physical Chemistry, Vol. 76, N o . 24, 1.972
effect on this rate; a rate enhancement of -lo5 is observed between the substituents X = OCH3 and X = i-CaH,. The large decrease of the rate observed in the passage from a nonpolar and aprotic solvent like toluene to a polar and protic solvent like ethanol is consistent nith earlier studies on benzothiazolinic and indolinic spiropyrans.12-'* This decrease is related to a polar structure of the open form of these compounds stabilized in ethanol by €3 bonding and by the high polarity of the solvent. These solvent-photomerocyanine interactions must be very large if we consider the difference of a factor of about 1000 observed on the decoloration liixietics in those two solvents. We will discuss now the structure effects on the decoloration rates in terms of charge and its delocalization. Alkyl substituents induce both a polar and a steric effect. Three types of substituentr have been used: alkyl or alicyclic, para-substituted aryl, and functional groups. First Tie consider the polar cfftlct of the substituent. By using the CS* paramelcrs as defined by Taft, we observe that the stability of'thcse compounds is sensitive to polar effects. The fading rate varies by a factor of 10 between CHs (cr* = 0.00) and CJ3, (CS*= -0.10) substituents; with an isoprcpyl groap (.* = -0.19) the rateincreasrs bya factor 30. This important variation of the kinetic rate is due to tlsc intervention of the steric effect (E, = -0.47 for t-C3X$7 nhereas E , parameter values are comparable for CII, and C2&, respectively, 0.00 and -0.07). This steric effect sensitivity appears much more clearly with the cyclohexyll substituent (Es = -0.79) which has a kinetic rate near that of isopropyl but its CScoefficient (-0.13) lies between CS*of z-Pr and ethyl substituents. Thew results show that steric effects arc determinant in the ring closure kinetic rates of the photomcrocyanine form; the rate increases as the groups in the 3 position become more bulky. To evaluate this steric interaction arid l o determine the most stable configuration for the photomerocyanine form, theoretical computations have been made s$iththe Symon's program taking account of van dcr Waals nonbonding interactions. l5 These computations have shown that among the various possible cis and trans configurations for these compounds. two trans structures A and B are favored. A theoretical conformational investigation using the Extended Huckel method has been developed on the
+
(12) R. Guglielmetti, M. Mosse, J. Ch. Metras, and J. RIetzger, J . Chim. Phys., 65,454 (1968). (13) 0. Chaude, Cah. Phys., 51,22 (1954). (14) J. €3. Flannery, J . Amer. Chem. Soc., 90,5660 (1968). (15) A . Samat, R. Guglielmetti, Y . Ferre, H. Pommier, and J. Metzger, J . Chim. Phys., 69, 1202 (1972).
3557
PHOTOCHROMIC 3-SUBSTITUTED BENZOTHIAZOLINIC SPIROPYRANS
X la
B
quinonic structure of the more stable A configuration for determining the rotation angle e which corresponds t o the minimurr energy.
+
relation1' log k / k o = p ( u rAu), where p is the reaction parameter, u is the inductive constant of the substituent, A u = 'u - u is the resonance contribution of the substituent effect as defined in the reference reaction of Brown and Oltamoto,ls and r is the degree of resonance interaction between the substituent and the reactive center in the studied reaction. The computation of this relation with a multiple regression program gives log k / k o = 1 . 5 0 ( ~ 0.27Au) with a Correlation coefficient R = 0.997. The value obtained for ~ ( 0 . 2 7 ) confirms the very weak degree of the resonance intcraction of the para sl.tbstituent, which is related to the large rotation of aryl groups with respect to the plane of electronic delocalization. The colored form of methoxy and phenoxy derivatives is largely stabilized when compared t o their methylthio and phenylthio homologs. In addition to the electronic and steric effects, a supplementary factor of stabilization may be proposed for oxygen coniparatively with sulfur: an intramolecular chelation by 13 bonding.
+
The rotation angle 8 increases with volume of the substituent (50" for 14, 70" for CH,, 75" for i-GH,). These resultb are compatible XTith the experimental observations on thc destabilization of the open form w t h increasing ~f hindrance of the 3-position substituent. To deterniiric the rlectronic contribution to the whole qubqtituent effect it is necessary to keep conitant the large steric interaction For this investigation, we have \elected para-substituted aryl groups CEHdX with X = H, CE,, OCH,, OH, C1, Br, and F for which steric effect.. may be cm.;idered as invariant. I n this serics of sLbstituents thc variation of reactivity has t o be related tc the sensitivity to elzctronic effects. It appears that the stability of the photomerocyanine is governed by inductive anti mmnance effects of the para X substitumts nhich transmitted to the carbon atom in the a position of tke ztryl group. Using the u para constants dcfined by Hammett, ]\e have obtained a linear relaf ionship (coefficient correlation R = 0 973) betneen reactivity and substitucnt effect (Figure 2) The slope (i-1.21) of this rclarion indicates that a positive charge density is l o c a t d on the atom 3 .
The existence for a up relationship for 3-position siibRtifuents har; to be compared l,o a uD+ relationship for 6' substitution [n the latter case, the strained planarity of thc nioiecule involves a maximal resonance interaction betm cen substituents and reaction center. IQthe former case, however, the steric hindrance leads to rotation of a 3-subrtituted para-aryl group out of the plane defined by tbc charge atoms Cz,Ca, and Cq. This very n ~ a kdcgree of conjugation for 3-position qJbstii;uents c2n be estimated by a Yukawa-Tsuno 12b18
I n this series of compounds, the study of the X = H derivative would be of major intercst, but this compound exists only in its open merocyanine form. This infinite stability must be related t o the absence of steric effect and hence to a maximal c ~ n j u g a t i o n . ' ~
I
I
- 0.3
- 03
L.
0.1
( J
P
Figure 2. Log IC = f(u,) toluene, 25' (16) R. Guglielmetti, Sciences Thesis, Marseilles, 1967. (17) Y .Yukawn and Y. Tsuno, Bull. Chem, SOC.Sap., 32, 965 (1959);
32,971 (1959). (18) E. C. Brown and Y. Okamoto, J . A m e r . Chem. Soc., 80, 4979 (1958) ; 79, 1913 (1957). The Journal of Physical Chemistry, Vol. 78, X o . 2.6, 1978
JEROME L. ROSENBERG AND IRA BRINN
3558 Moreover the comparison between X = H and X = SCH3 substituents argues for the determining influence of steric effects on stability of photomerocyanine when compared to electronic effects. Although the u polar constant3 are the same for these two substituents (uH = “3CR3 = O ) , an important rate of fading is observed for the SCH3 derivatiw (k200 = 76 sec-I in toluene).
Conclusion The investigation of the thermal fading kinetics for these 17 h u b s t i t u ted benzothiazolinic spiropyrans in ethanol and toluene solvents shows the important electronic delocalization developed in the colored photomerocyanine structure of
I
6-
This electronic delocalization is responsible for the influence of the polarity of the solvent on the fading rate of the photomerocyanine. In agreement with theoretical calculations the steric effect in the 3 position is of major importance in the nonplanarity of the molecule and in the destabilization of the colored photornerocyanine form.
Acknowledyment. We are grateful for support of this work by the D.R.hII.E, Optical Division 75996, Paris Armhes.
Excited State Dissociation Rate Constants in Naphthols by Jerome L. Rosenberg and Ira Brinn*l Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylzania
16115
(Received February 1 , 1972)
Pzihlacation costs assisted bg the University of Pittsburgh
Experimentally determined proton dissociation (and reassociation) rate constants for substituted naphthols in the first excited singlet state are reported. The results are rationalized on the basis of a charge-transfer explanation supported by CND0/2 and PPP molecular orbital calculations.
I. Introduction It has long becn known that the dissociation constant of an organic acid is dependent on the clectronic htatc of the n i o l ~ i i l e . Tm o possible explanations for this phenomenon have been advanced: (1) the acidity is related to some gross orbital feature of the state reflccted in t hc symmetry of its nave function;2 and (2) a more suhtle aspect of electronic rearrangement is involved such a5 a hmall change in charge-transfer charactcr.3 The first explanation has been sho\+n to be an oversimplification by the work of- Vander Donclit and P o r t ~ rwho , ~ showed that the excited singlet and triplet htates of anthrols, where both states are dcrived from sates o’ the same symmetry, still have appreciably different acidities. Proton dissociation and reassociation rate constants have previoiisly been reported5 for 2-naphthol. I n this paper n report c.xperimentally determined proton dissociation and rcassociation rate constants for 1naphthol, 2-naphthol, and various substituted naphthols in the first excited singlet state. The results arc rationalized on the basis of a charge-transfer explana(1
T h e Journal of Physical Chemistry, Vol. 7 6 , N o . 24, 1979
tion supported by CNDO/Z and PPP molecular orbital calculations.
11. Experimental Section A . Materials. The water used was filtered through both a Barnstead mixed bed ion-exchange column and a Barnstead organic removal column. The following naphthols were used : 1-naphthol and 2-naphthol (Eastman reagent), 2-cbloro-l-naphthoi1 4-chloro-lnaphthol, 1-bromo-2-naphthol, B-bromo-2-naphthol, and 1-chloro-%naphthol (K & K Laboratories 95(1) Correspondence should be addressed t o Departamento de Bioqufmica, lnstituto de Bioci&ncias,Universidade Federal de Pernambuco, Recife, Permambuco, B r a d . This article is based in part on a dissertation submitted by I. B. in partial fulfillment of the requirements for the Ph.D. a t the University of Pittsburgh in 1968. (2) T . Forster, “Reactivity of the Photoexcited Organic Molecule,” Interscience, New York, N. Y . ,1965, p 111. (3) J. N. IMurrell, “The Theory of the Electronic Spectra of Organic Molecules,” Methuen and Co., Ltd., London, 1963. (4) E. Vander Donckt and G . Porter, T r a n s . Faraday Soc., 64, 3218 (1968).
(5) (a) L. Stryer, J . A m e r . Chem. Soe., 88, 5708 (1966); (b) N . M. Trieff and B. R . Sundheim, J . P h y s . Chem , 69, 2044 (1965); (c) A. Weller, 2. P h y s . Chem. (Frankfurt a m M a i n ) , 3. 238 11956).
