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Naol4-76-C-o745-06 -- _____________________________4. TITL.E ( 1d $uOlftg.? - - ------- _~~~_ .- - S. TYP OF RIPOWrO PERIQOCOVERID /

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)chemically Initiated Electron Exchange Luminescenc Technical ~. ~~~. T~ (.. ~~~~~~~~~~~

~~~ A New Chemiluminescent Reaction Path for Organic ( _________________________

Peroxides. - ‘ PEAFONMINGORO. REPORT NUMBIN

7. AU~~HO~~~~~~ S. CONTRACT OR GRAN~ NUMSER(.)Gary B. /Schuster / -

Ja-youngjKoo ~~. I~~dO14-76-C-Ø745 /~~~~ ~~~~~~~-~~~~~~~~~~ - —

• © S. PERF~~qM.NO ORGA NIZATIO N lAM E AND AOOREU ID. PROGRAM ELEMENT. PROJECT . TASK

Department of CherHistry •_ •-•~~~~~~~~~ AREA S WORIC UNIT NUMBERS

~~~ University of Ill inois -

/ NR-05 1-616

~~~ Urbana , Ill inois 61801 /_ ___________________________

I I . CONTROUJNO OFFICE NAM E AND ADDRESS .IL ..Rg~ QRT DAT~

~~ Chemistry Program , Materials Science Division(,!~/ ‘ — May ~~~~~77• Office of Naval Research, 800 N. Quincy St.,

Arlington , VA 22217 __________________________

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IS. SUPPLEMENTARY NOTES

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II. KEY WQAO S (Ca,1h.v. ~ a r v r * ~ •lds SSn......p atd Ids.fi ~ ~~ ‘. Mock n~~ bsr) i .

Chemiluminescence ~ ~~ 2 ~~Radical Ion RecombinationOrganic Peroxide ~ 7

~~—.. Aromatic Hydrocarbon

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Q ~~The theruial decomposition of diphenoy1peroxide~ in the presence of certain

aromatic hydrocarbons generates benzocoumarin (~~~~

‘ and light corresponding to

LJ.J the fluorescence spectrum of the hydrocarbon. rt is shown that this chemilumi-_ j nescence does not result from conventional energy transfer from some electron-

~~~ ically exc i ted peroxide decomposition product to the aromatic hydrocarbon. In-stead, the chemiluminescence is initiated by elec tron transfer from the hydro-

a ~ carbon to the peroxide fol lowed by rapid decarboxylation and back e1ectron ,,,_~~

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transfer to form the electronically exci ted hydrocarbon . The yield of ligh tfrom this process is qu i te hi gh. It is suggested that a similar mechanismmay be operating in several previously described chemilum inescing systems.

Qi~ _ Q~~o+ ArH

~~~ + CO2 + ArH*

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OFFICE OF NAVAL RESEARCH0

Contract NOO14-76-C-0745

Task No. NR-051-616

TECHNICAL REPORT NO. NOthl4~76~C~O745~O6

Chemically Initiated Electron Exchange Luminescence.

A New Chemilumines cent Reaction Path for Organic Peroxides.

by

Gary B. Schuster and Ja-young I(oo

Prepared for Publication

t • in

Journal of the American Chemical Society

School of Chemical SciencesUniversity of Illinoi sUrbana , Illinois 61801

May 23, 1 977

Reproduction in whole or in part is permitted for-•

any purpose of the united States Government

Approved for Public Release; Distribution Unl imi ted.

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JUN 2 1911

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~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

by

Ja-young Koo and Gary B. Schuster*

Department of Chemistry

Roger Adams Laboratory

Universi ty of Illinois

Urbana , Illinoi s 61801

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Chemicall y Initiated Electron Exchange Luminescence.WVVWVV /VVW WVWW~~AA/WWV ~

• A New Chemiluminescent Reaction Path for Organic Peroxides.‘VVVVVt/VVVVVVVVVV1A/VV~/ VVt/VVVVVVVV / ~/ ~fVV\JVWVVVVWVlJVVVVVV’/ V~.

by

Ja-young Koo and Gary B. Schuster*

The thermal decomposition of diphenoyl peroxide in the presence

of certain aromatic hydrocarbons generates benzocoumarin (2) and light

corresponding to the fluorescence spectrum of the hydrocarbon. It is

shown that this chemi l uminescence does not result from conventional energy

transfer from some electronically exc ited peroxide decomposition product

to the aromatic hydrocarbon. Instead , the chemiluminescerrce is initiated

r~Th 0

+ ArH + CO2 + i%rH*

by electron transfer from the hydrocarbon to the peroxide followed by rapid

decarboxylation and back electron transfer to form the electronically exci ted

-• hydrocarbon. The yield of light from this process is quite high. It is

suggested that a similar mechanism may be operatinq in sev2ral previously

described chemiluminescing systems.

I

We would like to report an efficient new chemi lumi nescent reaction

that delineates an apparently important class of chemi l uminescent processes

and provi des insigh t into several previously reported light producing reactions.

In general , the exothermi c decomposition of peroxides to di rectly generate

electronically exci ted state carbonyl compounds has formed the basis for

nearly all of organic chemi l umi nescence.1 In this coniiiunication we will

outline a reaction sequence in which diphenoylperoxi de ( ) undergoes chemi cally

initiated electron exchange with an aromatic hydrocarbon to directly form the

electronically excited singlet state of the hydrocarbon whi ch , in turn, emi ts

a photon of visibl e light.

Thernulysis of a di l ute solution of diphenoylperoxi de2 in CH2C1 2 at ca.

24° for 24 hr resulted in the formation of benzocoumarin (2) in 75% yield 3a

and polymeri c peroxide , (equation 1). Under these condi tions there was

virtually no chemiluminescence from this reaction . However , addition of

çu%0 _(5

+C0 2 + Polymer (I)

certain aromatic hydrocarbons (see Fi gure 2) to the reaction mi xture resulted

in efficient light formation. The spectrum of the emission corresponds in all

cases to the fluorescence of the added hydrocarbon.

Such an observation is not unique among chemi l umi nescent systems and

has been attributed to electronic energy transfer to~~he added hydrocarbon from

a produc t molecule formed in an excited state. However, in this case, the unusual

I

p. p - - - ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - -• - - -.-•- —---- -- - _---•-•---~ - _______________________3

observation was made that while 9,lO-diphenylanthracene (DPA) was quite

effective at promoting light fo rmation , 9,10-dibromoanthracene and biacety l

were essent ially completel y ineffective . t~ Moreover, incorporation of the aromatic

hydrocarbon in the reaction solution increased the rate of cons umption of

the di phenoylperoxide. These observations indicate a special interaction

of the aromatic hydrocarbon wi th the peroxide rather than simple energy

transfer as the light forming step .

The chemi l uminescence observed from peroxide )~, and aromati c hydrocarbons

is strictly fi rs t order in peroxide concentration for more than 5 half-lives .

The effect of added aromati c hydrocarbon on the observed rate constant is

fi rst order in hydrocarbon and can be represented by a simple kinetic

expression , equation 2, where k~ is the rate constant for the unimolec ular

reaction and k2 for the hydrocarbon dependent reaction.

kobs = k~ + k 2 [Aromatic Hydrocarbon] (2)

Addi tional evidence that the chemi l umi nescence is a result of the

LI bimolecular reaction is revealed by the effect of aromatic hydrocarbon

concentrati on on the emi tted light intensity . If the unimolecular reaction

is responsible for ligh t generation , then at high hydrocarbon concentration ,

where nearly all of the peroxi de reacts by the bimolecular path , the hydrocarbon

should act as a quencher of the chemi l umi nescence. Fi gure 1 , a reciprocal

plot of intensity against concentrati on , shows that the chemi l uminescent

intensity is a linearly increasing function of the aromati c hydrocarbon

concentration even when greater than 90% of the reaction of )~ proceeds

through the bimolecular path. Thus , for the cases studied , the formation

of light must, be a consequence of the reaction of aromatic hydrocarbon

with ground state peroxi de.

~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~ ~~.—. • —-

~~~~~~~~~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ ~~.0 ~~~~~~~~~~~~~~~~~~ -. . -.~~~~~‘‘. ~~~~~~~~~~~~~ -~~~‘— •— — —--••—-_—-. — t___s___ th _. ~~~-%- - -

•_••_••__• __•_ _~__

~_••_~~~~~~ —

The nature of this interaction was probe d by examining the effect of

hydrocarbon structure on the rate constant for the bimolecular reaction.

Figure 2 shows a plot of the observed first order rate of chemi l umi nescence

dec ay against hydrocarbon concentration according to equation 2 for a series

of hydrocarbons. As predi c ted by equation 2 , all of the hydrocarbons pass

through the same intercept (kj , however, the slopes (k 2) are strongly

dependent on the structure of the hydrocarbon. Figure 3 shows a plot of

the natural log of k 2 against the one electron oxi dati on potential of the

aromatic hydrocarbons. The excellent correlation between the observed rate

and the oxidation potential indicates that the initiating step in the

chemi l uminescent process is an electron transfer frori the hydrocarbon to the

peroxi de.5 In the scheme below , we suggest a mechanism for this chemi l umi nescent

reaction consistent with our observations .

+ A rH k 2 , ~~~~~~~~~ ArH

+]

•

.

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

ArH + CO2 A rH +

o~~ 0

Light

• -i.. - — •.o__~~- - -- ~~~~~~~~ ~~~ . a . . ( -0~ ..*S f~ - I ~-• ~~~~

-

• •. ..‘T~~. • - ~ • .

‘

~~~~ •— ~~~~~~~~~~~~~ ,-—.---- ,- •------- —- -• --—-- --- --- -.- --- - -.- - ~~~~• • - -~ ~~~~~~ --•~~~-~~~~~~~~~- -

F! -

~~~~~~

_ ____

_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

Induced decomposi ti on of peroxidic compounds by nucleophi les 6 and redox

metals 7 is well known . Studies of the electrochemi cal reduction of diacy l

peroxides indicate that the electron transfer is i rreversible .8 In the case

under study the cage radical ion pair formed by the initial electron transfer

from the hydrocarbon to the peroxide has a facile reaction path available.

Decarboxylation followed by carbon oxygen bond formation results in the

radi ca l anion of benzocoumarin. We have determined that the reduction

potential of benzocoumarin is -1.92 eV (vs. SCE).~3 Thus , back electron

• transfer from the radical anion of 2 to the radi cal cation of the aromatic

hydrocarbon is sufficiently exotherrnic to generate the electronically

exci ted singlet state of the hydrocarbon. Such reactions have been observed

to generate light during electrogenerated chemi luminescence .10 An importan t

key feature of this new chemi l uminescen t mechanism is the rapid chemical

reaction of what was a very easily reduced compound to form a strongly

reducing species wi thin the solvent cage.

The total yield of electronically excited states for this reaction should be

sensiti ve to a nuni~er of factors such as the nature of the hydrocarbon , the

rate of decarboxylation , the cage lifetime , the solvent polari ty , and the excited

state yield on back electron transfer. We have compared the chemi l uminescence

of wi th perylene to tetramethyldioxetane .’’ Preliminary results indicate that

for this sys tem the yield of photons is ca. 10 ± 5%. Thus , even though

the reaction has not been opti mi zed, the light yield is remarkably high .

Several previously reported chemi l uminescent reactions appear to be

proceeding by the proposed electron exchange mechanism. The well known

oxalate ester system is reported to be ~catalyzed” by aromatic hydrocarbons .’3

Chemi l uminescence from ci-peroxylactones appears to be strongly dependent

- • upon the nature of the aromatic hydrocarbon.’~ The reaction of phthaloyl

t’.

I

_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ I

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

peroxide almost certainly proceeds by the proposed mechanism .15 Our recent

report of chemi l uminescence from a suspected cyclic diacy l peroxi de fits this

interpretation.16 Chemi cally initiated electron exchange l uminescence may be

a general phenomenon responsibl e for many chemi- and bioluminescent reactions.

Further efforts to unravel the details of these chemilumirrescent processes

and probe the generality of this mechanism are underway.

Acknowledgement. We wish to thank Professor Faulkne r of this Departmentwvvvvvww’1w’~

for the determination of the reduction potential of benzocoumari n and for manyhelpful discussions . This work was supported in part by the Offi ce of Naval

Research and in part by the donors of the Petroleum Research Fund, administered

by the American Chemical Society .

3

‘ - I

I

_ _ _ _ _ _ _ _ _ _ _ _

_________

_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

i•i~

~~~~~ -— ---.- - __~7~~

— -

~~~

-—

~~~~~~

References and Notes• ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

1. (a) F. McCapra , P!~gr. Org. Chem., 8, 231 (1973); (b) A notabl e exception

is Dewar benzene , P. Lechtken , R. Breslow , A. H. Schmidt , and N. J.

Turro , J. Am. Chem. Soc., 95, 3025 (1973).

2. The cyclic diacyl peroxide 1 was prepared by the ozonolysis procedure ofRamirez , F. Ramirez , N. B. Desai , and R. B. Mitra , J. Am. Chem. Soc., 83,

492 (1961). Purification was accomplished by repeated recrystallization

from MeOH/CH2C1 2 at -20° and gave pale yellow needles that decomposed at

Ca. 73°. Mol ecular weight determination by vapor pressure osmometry

indicated that the compound was monomeric and peroxide titration

showed that it was at least 95% pure .

3. The isolated benzocoumarin was identical to an authentic sampl e ,

D. G. Mehata and P. N. Pandry , Synthesis, 404 (1975).

4. (a) Singlet—singlet energy transfer to DPA and OBA should be about

equally efficient since they have the same singlet energies ; see

S. P. McGlynn , T. Azumi , and M. Kasha , J. Chem . Ph,ys., 40 , 507 (1964)

and I. Beriman , “Handbook of Fl uorescence Spectra of Aromatic Molecules ,”

Academic Press , London , 1 965; (b) Triplet—tri plet energy transfer to the

low energy triplet of biacetyl should have generated the phosphorescent

triplet state of this molecule , K. Sandros , Acta Chem. Scand. , 23 , 2815

(1969).

-• 5. W. L. Reynolds and R. W. Lumry, “Mechanisms of Electron Transfer,”

Ronald Press, New York, N.Y., 1966.

6. For exampl e see: F. 0. Greene and W. W. Rees, J. Am. Chem. Soc ., 80,

3432 (1958).

7. J. K. Kochi and H. E. Mains , J. Org. Chem ., 30, 1862 (1965).

1 8. 0. A. Skoog and A. B. H. Lauwzecha , Anal. Chem., 28 , 825 (1956).

~~~~~~~- • T • L~11~1 ~i::~’ •J

- V. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

— - • - •-_

1

8

9. The reduction potential was determined by cyclic voltammetry .

10. L. R. Faul kner , m t . Rev. Sci . : Phys . Chem ., Ser. Two , ~, 213 (1976).

2 11. We assumed the literature value for the yield of excited acetone from

tetramethyld ioxe tane of 30% .12 A large part of the uncertainty in the

li ght yiel d is a result of working at very dilute acceptor concentra-

tions to avoid self-abso rption .

12. 1. Wilson , D. F. Golan , M. S. Harris , and A. L. Baumstark , J. Am. Chem.Soc. , 98 , 1086 (1976).

1. 13. M. M. Rauhut , Accts . Chem. Res., 2 , 80 (1969).

14. W. Adam , G. A . Simpson , and F. Yany , J . Phys. Chern., 78, 2559 (1974).

The suggestion that the chemiluminescence results from triplet-tripleta

annihila tion of rubrene in air saturated solution is internally

- inconsistent . The triple t energy of rubrene must be more than

half the singlet energy in order to form light by this path , and this

quantity is greater than the tripl et-singlet transition energy of

oxygen .

15. K. -0. Gundermann , M. Stenfatt , and H. Fiege , An~~w. Chern. internat.

Edit.. 10 , 67 (1971).

16. G. B. Schuster. ,J. Am. Chem. Soc., 99, 651 (1977).a’-” ,

17. V. D. Parker , J . Am. Chem . Soc., 98, 98 (1976); A. J. Bard , Discuss.

- P - Faraday Soc ., 45, 167 (1 968); C. K. Mann and K. K. Barnes , “Elec tro-

chemical Reactions in Nonaqueous Systems,” Marcel Dekker , New York ,

i~. New Yo rk , 1 970.

1ii

~~~~~~~~~~~~~~~~~~~~ ~~~ ••±::: L

. A ;.~ :~:_2T~ :~~

•

~~~~on’,~A,~~~~~~

ures

Figure 1. Reciprocal plot of chemi l uminescence intensity aqainst DPA

concentration in CH2C1 2 at 32.5°; [1] = S x lO~~ M.

-

~~~~~~ Effect of added aromatic hydrocarbon concentration on the

reaction rate for peroxide 1 in CH~Cl2 at 32.5°; [1] = 5 x l0~~ M.

Figure 3. Correlation of log k 2 and oxidation potential 17 for the chemically‘vVv~fvvvb -

initiated electron exchange l uminescence of perox ide 1. Note that the

point numbers correspond to those in Figure 2 and that is pyrene.

,1

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No. Copies

Dr. C: B. SchusterChemis tr ~r DepartmentUniversity of Il linois

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