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Determination of the kinetic rate constants associated with pyrene and DMA exciplex formation and decay
Serena Xu, Leah Foscaldi, Michael Stanowski, and Jackie Guo Department of Chemistry, The Pennsylvania State University, University Park, PA 16802 Su mitte!" #ar$h 1%, 201& 'C()# %*+, Se$tion &,

A stract
The kinetics of pyrene and DMA exciplex formation and decay were studied through the use of time-resolved laser photolysis in solutions of 10M pyrene and 0 ! and

" mM DMA in decane and excitation wavelengths of #$$ nm% &rom these data sets the rate constant for the singlet excited state pyrene decay was determined to 'e (!%)0*0%001+x10$s-1 the rate constant for the formation of the exciplex was determined to 'e ($*0%$+x10,M-1s-1 and the rate constant for the decay of the exciplex was determined to 'e (1%,*0%#,+x10 -s-1% The rate of dissociation of the exciplex into singlet excited state pyrene was determined to 'e negligi'le% These results are important in the analysis of any of
the many experiments that utili.e the long lifetime of the pyrene exciplex and singlet excited state pyrene%

!ntroduction &luorimetry and laser photolysis can 'e used to study complex kinetic systems and to determine rate constants for these systems% /ne example would 'e polycyclic aromatic molecules like pyrene (0y+% 0yrene can return from an excited state to a ground state through several pathways which

include fluorescence decay from a singlet excited state (10y+ and fluorescence decay from an exciplex (12x+ form where it has reacted with DMA% 1 0reviously the fluorescent properties of pyrene have 'een used in many experiments due to the long lifetime of its excited state% &or example 3uki 4ayasho demonstrated the a'ility to monitor the movement of polymer segments at a polymer-silica interface 'y studying the decay of singlet excited state pyrene and the exciplex where pyrenyl was linked to the silica and the polymer was coated with DMA%! 5round state pyrene can 'e excited 'y 67 light to a singlet excited state (reaction 1+ from which it can decay with fluorescence in a singlet state (reaction !+% At high ground state pyrene concentrations singlet excited state pyrene can also form an exciplex 'y reacting with dimethyl aniline (DMA+ (reaction #+% As a heterodimer the exciplex will decay with fluorescence to ground state pyrene and DMA (reaction "+% The rate constants k0 and k! represent the rate of decay of singlet excited state pyrene and the exciplex respectively% k1 represents the rate of formation of the exciplex from singlet excited state pyrene and DMA while k-1 represents the dissociation of the exciplex to singlet excited state pyrene% 0y 8h9 10y
k0

10y 0y 8h9M
k1 k-1

(1+ (!+ (#+ ("+

10y 8 DMA 12x

k!

12x

!0y 8 h92

The kinetics of this system can 'e descri'ed as a pseudo first order system 'y e:uations (1+ (!+ and (#+ if k-1 is assumed to 'e negligi'le%

(!+

6sing these e:uations ko's was found from the slope of lineari.ed luminescence decays of singlet excited state pyrene in e:uation (1+% ko's represents the sum of the rate of fluorescence decay k0 and the rate of reaction with DMA to form an exciplex k1 (see e:uation !+% The rate of decay of 12x was then determined 'y fitting e:uation , to the excimer luminescence traces using previously determined rate constants% 1 ;t was important in this experiment to use a <excitation of #$$nm 'ecause lower wavelengths are a'sor'ed too easily 'y pyrene resulting in a concentration gradient of excited state pyrene% =uch a concentration gradient would make the kinetics much more complex%# "xperimental Description ;n a procedure modified from that 'y >ratol?u' Milosavl?evic
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three

samples of constant ground state pyrene concentration (10M+ and varying

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DMA concentration (0 ! " mM+ in decane were created and purged with nitrogen% An emission spectrum of each sample was taken (see figure 1+ on a 4ori'a @o'in 3von &luorolog with <excitationA#$$nm% 6sing the setup in &igure 1 luminescence decay was taken for all three solutions with a #)0*, nm filter and again for the ! and " mM DMA solutions with a ,00 nm filter%

F!G#$" %& "xperimental Setup, 'ektronix 'DS ()*+, Di-ital .hosphor /scilloscope

$esults The three emission spectrums were normali.ed with respect to the third vi'rational peak in the monomer spectrum (see figure !+% ;n figure # the emission from the singlet excited state pyrene can 'e seen from a'out #,0 to "00 nm while the emission from the exiplex is 'roader and at a higher wavelength from a'out "00 to ,00 nm% The increase in excimer emission with increasing DMA concentration can 'e seen in &igure " where the 0 mM DMA emission spectrum is su'tracted from the ! and "mM DMA emission spectrums to yield the exciplex emission spectrum only%

F!G#$" +

F!G#$" (

F!G#$" 0

The luminescence decays for all three samples with the #)0*, nm filter were normali.ed and plotted together against time in &igure ,% These represent the relative intensity of the emissions from the singlet excited state pyrene% 2ach was lineari.ed and fitted with a line (see &igure $+ whose slope represents ko's (see &igure )+ as in e:uation 1%

F!G#$" * The ko's were plotted against DMA concentration (see &igure -+% The slope k1 and the y-intercept k0 (see e:uation !+ were found to 'e ($*0%$+x10,M-1s-1 and (!%)0*0%001+x10$s-1 respectively%

F!G#$" 1

DMA ,oncentration 2mM3 0 ! " F!G#$" 5

ko

2s4%3

(!%$0*0%00#+ x10$ (#%B#*0%00"+ x10$ ("%-!*0%00$+ x10$

F!G#$" 6 k-1 the rate of the dissociation of the exciplex to the excited state pyrene and DMA was determined to 'e negligi'le% The emission spectrum (see figure #+ clearly indicates that the exciplex emission is at a higher wavelength and therefore lower energy than the singlet excited state pyrene% Thus the dissociation reaction in the k-1 direction is highly unfavora'leC dissociation re:uires an increase in energy while decay results in a decrease in energy% ;n addition it can 'e seen in figure , that when DMA increases the emission from singlet excited state pyrene decreases more :uickly indicating that a significant amount of the pyrene decay occurs as part of an exciplex% Gire

F!G#$" 7 &igure B shows the normali.ed luminescence decays from the !and "mM DMA samples with a ,00nm filter which represents the decay from the exciplex through !00ns and shows that the laser is fast enough to monitor excimer formation and that the results of the luminescence decays are not artifacts caused 'y continuous excitation% The rate of decay of 12x was then determined 'y fitting e:uation , in MATDA> to the excimer luminescence traces in &igure B using the previously determined rate constants% k! was determined to 'e (1%,*0%#,+x10-s-1% Discussion k0 k1 and k! were previously found to 'e !%0E10$ sF1 B%-E10BMF1 sF1 and ,%#E10$sF1 respectively for solutions of pyrene and DMA in cyclohexane%" These differ from the rate constants k0 k1 and k! determined in this experiment 'y !$G 1 $## !00G and B$G% The differences likely result from the fact that the previous experiment used an excitation wavelength of ##) nm% 0yrene a'sor's waves of this length much too readily resulting in a

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strong concentration gradient as descri'ed in the introduction% Honhomogeneous distri'ution of excited state pyrene molecules can make the system very hard to model 'ecause pseudo first order kinetics will not apply due to second order kinetics non-homogeneous diffusion and singletsinglet annihilation% ;f pseudo first order kinetics are used to represent the system anyway errors in calculated rate constants will result%# This means that the results of this experiment are likely more accurate than those of the previous and corro'orates the claim that using a ##)nm excitation wavelength will result in faulty data%# The use of cyclohexane as a solvent instead of decane may also have contri'uted to the differences% Hew results for the rate constants of pyreneIDMA will help to improve any experiments that use pyrene exciplex fluorescence such as that 'y 4ayasho%! To improve the la' a larger range of experimental conditions i%e% higher concentrations of DMA could 'e used or This experiment is limited 'y the very small amount of exciplex that dissociates as well as the sensitivity of the oscilloscope and fluorolog used% The experiment was okay J values were found for each rate constant and all plots resulted in smooth curves that appeared as expected% 4owever the difference 'etween the experimental and literature values is enough to create dou't a'out their accuracy% ,onclusion To study the complex kinetic system of the formation and decay of the pyrene and DMA exciplex time-resolved laser photolysis was used to plot

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luminescence decays% &rom these data sets k0 the rate constant for the singlet excited state pyrene decay was determined to 'e (!%)0*0%001+x10 $s1

% k1 the rate constant for the formation of the exciplex was determined to

'e ($*0%$+x10,M-1s-1% k! the rate constant for the decay of the exciplex was determined to 'e (1%,*0%#,+x10-s-1% k-1 the rate constant for dissociation of the exciplex into singlet excited state pyrene was determined to 'e negligi'le% This data could 'e useful in the many experiments that utili.e the long lifetime of pyrene fluorescence% Acknowled-ements The author would like to acknowledge Deah &oscaldi Michael =tanowski and @ackie 5uo for their colla'oration on the experimental portion of this la' and teaching assistants >rian Konway and @ennifer Tan for their help% Literature ,ited
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Milosavl?evic >%4% Da' 0acket for K42M ",)L 2xperimental 0hysical Khemistry Pyrene Excimer Formation Kinetics% 6niversity 0ressL 6niversity 0ark !01!%
4ayashi 3%C Munihiro ;% Movement of 0olymer =egments 'y 2xciplex 2mission of 0yrene and H H-Dimethyaniline at the 0olymer-=ilica ;nterface% J. Fluoresc. +))( 13 ! 1!B-1#)% =pringerlink% httpLIIlink%springer%comIarticleI10%10!#G!&A G#A10!!B-!B!"BB!ND;AtrueOpage-! (accessed March 1# !01#+%

4anlon A%C Milosavl?evic >% Appropriate excitation wavelength removes o'fuscations from pyrene excimer kinetics and mechanism studies% Photochem. Photobiol. Sci. P/nlineQ% +)%( Advance Article% R=K 0u'lishing% httpLIIpu's%rsc%orgIenIKontentIArticleDandingI!01#I00Ic!pp!,#0)k (accessed March 1# !01#+% 3oshihara M%C Masuya T% Time resolved spectra of pyrene excimer and pyrene-dimethylaniline exciplex% Chem. Phys. Letters. P/nlineQ% %75% 9 , "$B-")!% =cience Direct%

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httpLIIwww%sciencedirect%comIscienceIarticleIpiiI000B!$1")1-0!)!,O (accessed March 1# !01#+%

Report Suestion
1% Honhomogeneous distri'ution of excited state pyrene molecules can

make the system very hard to model 'ecause pseudo first order kinetics will not apply% ;n samples with an excited state pyrene concentration gradient second order kinetics non-homogeneous diffusion and singlet-singlet annihilation may occur% ;f pseudo first order kinetics are used to represent the system when pseudo first order kinetics cannot apply 'ecause of a concentration gradient errors in calculated rate constants will result% (httpLIIpu's%rsc%orgI2nIcontentIarticlepdfI!01#IppIc!pp!,#0)k+