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9 -1
A (x10 s )

-1
Ea (cm )

MeCN

5.38 ± 2.63

1197 ± 97

CH2Cl2

6.83 ± 2.22

1282 ± 62

-9 -1
Rate (x10 s )

15

10

5

200

220

240
260
Temperature (K)

280

300
!

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6
5

µeff

4
3
2
1
0
180

200

220

240

260

280

Temperature (K)

300

320
!

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ln(K) = -3.5317 (.0936) (1/T) - 895.4 (23.4)

0.0

ln (Keq)

-0.5
-1.0
-1.5
-2.0
-2.5 ln(K) = -3.3164 (.118) (1/T) - 1220.4 (29.6)
3.4
3.6
3.8
4.0
4.2
4.4
4.6

4.8

-3

Inverse Temperature (1/K) (x10 )

!
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[Fe(tren(6-Me-py)2(py)](PF6)2

6 -1

Rate (x10 s )

Acetone

2.5
2.0
1.5

!H = -895 ± 155 cm

-1

-1
!S = -3.53 ± 0.94 cm /K
-1
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1.0
0.5
200

220

240
Temperature (K)

260

280
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[Fe(tren(6-Me-py)(py)2](PF6)2

6

6 -1

Rate (x10 s )

Acetone

4

!H = -1220 ± 78 cm

-1

-1
!S = -3.32 ± 0.21 cm /K
-1
" = 7821 ± 158 cm
-1
Hab = 16 ± 3 cm

2

200

220

240

260

280

Temperature (K)

(

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12
[Fe(tren(py)3](PF6)2

6 -1

Rate (x10 s )

10
8
6

-1
!H = -1500 ± 500 cm
-1
!S = -3.5 ± 1 cm /K
-1
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-1
Hab = 20 ± 4 cm

4
2
200

220

240

260

280

Temperature (K)

!

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-1
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10000
9000
8000

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!H = -2000 cm
7000

20

30

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Hab (cm )

-1

40

50

10000

18
17
16
15
14
13

9000
8000

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-1

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7000

20

30

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18
17
16
15
14
13

-1
50

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Reorganization Energy (cm )

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10000 !S = -4 cm

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18
17

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9000

16

8500

15
14

8000

13

7500
7000

20

30
40
-1
Hab (cm )
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10000 !S = -3 cm
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18
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9000
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20

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-1
Molar Absorptivity (M cm-1)

15000

10000

400

Wavelength (nm)
500

600

700

800

2+
[Fe(terpy)2]
[Fe(tbterpy)2]2+
[Fe(adterpy)2]2+
2+
[Fe(maniterpy)2]
2+
[Fe(paniterpy)2]

5000

0

25000

20000
-1
Energy (cm )

15000
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!

"R!

Normalized Change in Absorbance

!

-0.2
-0.4
-0.6
-0.8
-1.0
0

4000
Time (ps)

2+
[Fe(terpy)2]
2+
[Fe(adterpy)2]
2+
[Fe(tbterpy)2]
2+
[Fe(maniterpy)2]
2+
[Fe(paniterpy)2]
8000
12000
!

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3%'+*%30B!
!
!

!

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120

-1
k (µs )

100
80

2+

[Fe(terpy)2]
2+
[Fe(adterpy)2]
2+

[Fe(tbterpy)2]
2+
[Fe(maniterpy)2]
2+
[Fe(paniterpy)2]

60
40
20
180

190

200

210
220
Temperature (K)

230

240

250
!

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Reorganization Energy (cm

-1
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10000
9000

!S = -2 cm

-1

!H = -1000 cm

8000

20
-1

19
18

7000

17

6000

16

5000

15

4000

5

10

15

20

Hab (cm

25

30

-1
)

Reorganization Energy (cm

-1
)

10000
9000

20
19

8000

18
7000

17

6000
!S = -5 cm
5000
4000

!H = -4000 cm
5

10

15

20

Hab (cm

-1
)

16

-1

25

15

-1

30

!

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Reorganization Energy (cm

11000
18
10000
9000

!S = -2 cm

-1

!H = -1000 cm

17
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16
15

8000

14

7000

13
6000
10

15

20

25

Reorganization Energy (cm

-1
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Hab (cm

30

35

40

-1
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11000
18

10000

17

9000

16

8000
7000
6000
10

15
!S = -5 cm

!H = -4000 cm
15

20

14

-1
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13

25
Hab (cm

30
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35

40

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-1
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10000
9000

!S = -2 cm

-1

!H = -1000 cm

20

-1

19
18

8000

17

7000

16
15

6000
5000
15

20

25

30

35

Hab (cm

40

45

50

-1
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Reorganization Energy (cm

-1
)

11000
10000

20
19

9000

18

8000

17
16

7000
!S = -5 cm

6000
5000
15

-1

!H = -4000 cm
20

25

30

35

Hab (cm

-1
)

40

45

15
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Change in Absorbance

!!!!!!!!!

Transient Absorption:

233 fs

Transient Absorption: 1000 fs
Calculated Difference: 17% excited state
350

400

450

500

Wavelength (nm)

550

600

!

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!

-3
Change in Absorbance (x10 )

400

200 fs
233 fs
266 fs
300 fs
400 fs
500 fs
1000 fs

10

5

0

-5
27000

26000

25000

-1
Energy (cm )

24000

23000

!

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&/):.&()'!'+9:/%1%5B!!!!

Normalized Change in Absorbance

-1
Energy (cm ) 25000

20000

18000

16000

terpy
tbterpy
adterpy
maniterpy
paniterpy

0.5

0.0

-0.5

-1.0
350

400

450
500
550
Wavelength (nm)

600

650
!

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#\#!

-3
Change in Absorbance (x10 )

!

3

terpy
tbterpy
adterpy
maniterpy
paniterpy

2
1

57 ± 15 fs
70 ± 15 fs
63 ± 15 fs
20 ± 10 fs
28 ± 10 fs

0
-1
-2
0.0

0.5

1.0

1.5
Time (ps)

2.0

2.5

3.0
!

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-3
Change in Absorbance (x10 )

(

3
terpy
tbterpy
adterpy
maniterpy
paniterpy

2
1

57 ± 15 fs
70 ± 15 fs
63 ± 15 fs
20 ± 10 fs
28 ± 10 fs

0
-1
-2
-0.2

0.0

0.2
Time (ps)

0.4

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1
0
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0.0

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Molar Absorptivity (M cm )

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10000
8000
6000
4000
2000
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28x10

3

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3

800x10

Intensity

Intensity (S/R)

600

4
3
2

400

650

700

750

800

Temperature (K)
Emission Scan
200

0
700

Excitation at 610 nm

720

740

760

780

800

820

Wavelength (nm)
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4000
3
3000
2

2000
1000

1
400

450

500

550

600

-1
-1
Extinction Coefficient (M cm )

5000

4

650

Wavelength (nm)
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1

-3
!A (x10 )

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Change in Absorbance (x10 )

3

3
2
1
0
-1
-2

0

0

-1
-2

[Fe(dkpp)2]2+
tau = 76 fs
IRF = 75 fs
0.0

0.5
Time (ps)

1

2
3
Time (ps)

1.0

4

1.5

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=4)!)%)*80).!,+*!/4)!/4*))!*)3!/*2%.0/0+%.!E#PB!%'6!(;&)!302'+%3Q!B"N!%'6!8*))%!50*5;)Q!
LHN! %'6! *)3! /*02%8;)G! 2*)! 0%! /4)! 12?);)%8/4! *)80+%! 14)*)! /4)! ')/2;K/+K;082%3! 542*8)!
/*2%.,)*! /*2%.0/0+%.! +,! '2%7! 0*+%E>>GK9+;797*037;! 5+'9;)@).! 299)2*<! $;+%8! 10/4! /4)!
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(2%3.<!=4)!(;&)!'+./!/*2%.0/0+%!EPBB!%'6!32*F!(;&)!.-&2*)G!0.!2!(0/!'+*)!2'(08&+&.<!=4)!
12?);)%8/4!*)80+%!0.!5;+.)*!/+!/42/!,+*!;082%3!;+52;0O)3!/*2%.0/0+%.6!(&/!/4)!0%/)%.0/7!+,!/4)!
/*2%.0/0+%!0.!;+1!,+*!!!!T!/*2%.0/0+%.<!M0/4+&/!/4)!3N!2%2;+86!/4)!2..08%')%/!12.!&%5;)2*<!
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9&'9!)%)*87!3)9)%3)%/<!U*+&%3!./2/)!*)5+?)*7!0.!.4+1%!0%!D08&*)!H<!=0')!5+%./2%/.!,*+'!
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D08&*)! P<! =1+! +(.)*?2/0+%.! 52%! ()! '23)! ,*+'! /4)! *).&;/.! +,! D08&*)! PV! ! ,0*./6! /4)! ()42?0+*!
,*+'!/4)!PBB!%'!)@50/2/0+%!0.!%+/!.0'0;2*!/+!/42/!+,!2;;!+/4)*!9&'9!12?);)%8/4.Q!.)5+%36!2!
?2*02/0+%!0%!;+%8!;0?)3!/*2%.0)%/!.08%2;!0.!)@50/2/0+%!)%)*87!3)9)%3)%/!,+*!/4)!/4*))!9&'9.!
0%!/4)!RSA=!*)80+%<!
!

Normalized Change in Absorbance

0.0

-0.2

-0.4

355 nm, 276.2 ± 1.3 ps

-0.6

620 nm, 283.6 ± 1.9 ps
-0.8

-1.0
0

200

400

600

800

1000

1200

Time (ps)
+.3,'&( )4@*( I01348.H&7( &F/.%&7( 2%#%&( 7&/#J( %'#/&2( 0;( <+&=7>$$?@A@B( KG.%"( 7.;;&'&1%(
&F/.%#%.01( &1&'3.&2E( L0%"( %'#/&2( G&'&( $'09&7( .1( %"&( &F/.%&7( 2%#%&( 98&#/"( #%( )MM( 1:(
;0'(NKK(1:(&F/.%#%.01(#17(K)M(1:(;0'()@M(1:(&F/.%#%.01E(

!

"#P!

!

Normalized Change in Absorbance

Pump:
355 nm
435 nm
510 nm
620 nm

1.0

0.5

Probe: 410 nm
0.0

-0.5

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Time (ps)
+.3,'&()4N*(-&/#J(%'#/&2(;0'(<+&=7>$$?@A@B(G.%".1(%"&(;.'2%(N($2(0;(&F/.%#%.01(G.%"(%"&(
.17./#%&7($,:$(&1&'3.&2E(O"&(98,&(;.%(8.1&(2"0G2(#(%.:&(/012%#1%(0;(5EMP(Q(MEM)($2E(R88(
%'#/&2(G&'&($'09&7(#%(S5M(1:E(
=4)!,0*./!+(.)*?2/0+%!52%!()!)@9;20%)3!(7!2..08%0%8!/4)!PBB!%'!(2%3!0%!/4)!2(.+*(2%5)!
.9)5/*&'!2.!;082%3!;+52;0O)3<!=4)!3)5*)2.)!0%!)@/0%5/0+%!5+),,050)%/!5+'92*)3!/+!/4)!!!!T!
/*2%.0/0+%.! +,! CD)E/)*97GHIHJ! +*! CD)E(97GPIHJ! 52%! ()! 3&)! /+! 0%/)%.0/7! ./)2;0%8! ,*+'! +/4)*!
/*2%.0/0+%.<!$330/0+%2;;76!/4)!.08%0,052%/!*)3K.40,/!+,!/40.!/*2%.0/0+%!52%!()!)@9;20%)3!(7!/4)!
0%5*)2.)! 0%! 5+%:&82/0+%! ,+*! /4)! 3F99! ;082%3! 2.! 5+'92*)3! /+! /)*97! +*! (97<! W0%5)! /4)! /4*))!
*)33)*!/*2%.0/0+%.!2*)!+,!+%)!/79)!2%3!/4)!(;&)./!/*2%.0/0+%!0.!+,!2%+/4)*6!0/!0.!%+/!.&*9*0.0%8!
/42/!/4)!/0')!5+%./2%/.!E+*!*);2@2/0+%!92/4127.G!1+&;3!()!30,,)*)%/<!
=4)! .)5+%3! +(.)*?2/0+%! 0.! /42/! /4)! ;+%8K;0?)3! .9)50).! 2,/)*! 542*8)! /*2%.,)*! )@50/2/0+%!
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'+*)!*)2.+%2(;)!/+!/40%F!/42/!"NNZ!+,!/4)!)@50/)3!'+;)5&;).!9+9&;2/)!/4)!0%0/02;;7!)@50/)3!
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./2/)<!D+*!/40.!*)2.+%6!%+*'2;0O2/0+%!2/!/4)!9)2F!+,!/4)!0%0/02;;7!)@50/)3!./2/)!2*+&%3!/YN!12.!
3))')3!255&*2/)!,+*!5+'92*0.+%.<!>/!0.!7)/!&%3)/)*'0%)3!14)/4)*!/40.!30,,)*)%5)!0%!;+%8K
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/+12*3!/4)!(;&)<!M0/4!;+1)*!9&'9!0%/)%.0/0).6!;)..!)@50/)3!./2/)!0.!)@9)5/)3!/+!()!5*)2/)3!
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)@50/2/0+%!)%)*87!3)9)%3)%/<!>,!4084)*!)%)*87!)@50/2/0+%!.+')4+1!*).&;/.!0%!;)..!;+%8K;0?)3!
9+9&;2/0+%! /42%! ;+1! )%)*87! )@50/2/0+%6! 2! .'2;;)*! +,,.)/! 1+&;3! ()! .))%! 2/! ;+%8)*! /0').! ,+*!
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70);3!./&37!1+&;3!42?)!/+!()!9)*,+*')3<!X)/O);!)@9;20%.!2!9*+5)3&*)!,+*!3)/)*'0%0%8!/4)!
70);3! ,+*! ;082%3! ,0);3! )@50/)3! ./2/).! &.0%8! CD)E94)%GPIHJ<"! $;/4+&84! /4).)! '+;)5&;).! 2*)!
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,+*! /4)! ;082%3! ,0);3! *);2@2/0+%! 9*+5)..).! +,! /4)! 0*+%! 5+'9;)@).<! $;/4+&84! .+;?)%/!
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);)5/*+%.!()/1))%!/4)!')/2;!0%!/4)!5)%/)*!2%3!/4)!;082%3!+%!9)*094)*7!+,!/4)!5+'9;)@!2%3!
.+;?)%/!'+;)5&;).!2*)!)@9)5/)3!/+!*).9+%3<!$%!)@/*2!F0%)/05!5+'9+%)%/!52%!.+')/0').!()!
+(.)*?)3! 0%! 3)527! /*25).! 2,/)*! 542*8)! /*2%.,)*! )@50/2/0+%6! 0%3052/0%8! 2! )%)*87! 30..092/0+%!
92/4127!3&)!/+!/4)!.+;?)%/<!=4)!.+;?2/)3!5+'9;)@!42.!2!92*/05&;2*!542*8)!30./*0(&/0+%!0%!0/.!
8*+&%3!./2/)!2%3!.+;?)%/!'+;)5&;).!+*0)%/!/4)'.);?).!/+!'0%0'0O)!/4)!)%)*87!*)-&0*)3!/+!
0%/)*25/!10/4!/40.!542*8)!30./*0(&/0+%<!R+?)')%/!+,!);)5/*+%.!,*+'!+%)!92*/!+,!/4)!'+;)5&;)!
/+!/4)!+/4)*!542%8).!/4)!542*8)!+%!/4)!;082%3!2%3!*)-&0*).!2!*).9+%.)!,*+'!/4)!.+;?)%/!/+!
*)30./*0(&/)! 0/.! +1%! 542*8).<! A42*8)! /*2%.,)*! /*2%.0/0+%.! 2*)! )@9)5/)3! /+! 0%50/)! 2! .+;?)%/!

!

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*).9+%.)!2%3!/4)!*).9+%.)!10;;!?2*7!10/4!.+;?)%/!/79)Q!9+;2*0/76!.0O)6!./*)%8/4!+,!0%/)*25/0+%!
2%3!+/4)*!.+;?)%/!542*25/)*0./05.!3)/)*'0%)!/4)!.0O)!+,!/4)!*).9+%.)<!!
M4)%!2!/*2%.0/0+%!3+).!%+/!0%?+;?)!;082%3.!2%3!0.6!0%./)236!;+52;0O)3!+%!/4)!')/2;!5)%/)*!
+,! /4)! 5+'9;)@6! 2! '&54! .'2;;)*! .+;?)%/! *).9+%.)! 0.! )@9)5/)3<! =4)! 542*8)! 30./*0(&/0+%!
5)%/)*.! +%! /4)! '033;)! +,! /4)! 5+'9;)@! 14)*)! .+;?)%/! 42.! ;)..! 0%/)*25/0+%! 2%3! 3+).! %+/!
542%8)! +?)*! /4)! 5+&*.)! +,! /4)! /*2%.0/0+%<! $.! .4+1%! 0%! D08&*).! "! 2%3! H6! 4+1)?)*6! 2!
.08%0,052%/!542%8)!0%!8*+&%3!./2/)!*)5+?)*7!*2/).!0.!.))%!10/4!?2*0+&.!.+;?)%/.<!=4)!/*)%3.!
2;+%8! /4)! .+;?)%/! .)*0).! 3+! %+/! .))'! /+! /*25F! 9+;2*0/76! 30);)5/*05! 5+%./2%/6! .0O)6! +*!
9*+/+%2/0+%<! >/! 0.! 9+..0(;)! /42/! /4)! .0O)! +*! .429)! +,! /4)! .+;?)%/! '+;)5&;).! 52%! ),,)5/! /4)!
2'+&%/! +,! 0%/)*25/0+%! 9+..0(;)! 10/4! /4)! ')/2;! 5)%/)*! 2.! /4)! ;082%3! ,0);3! /*2%.0/0+%! /2F).!
9;25)<! >%! +*3)*! /+! 3)/)*'0%)! /4)! 52&.)! +,! /4).)! ?2*02/0+%.6! 52;5&;2/0+%.! 2*)! &%3)*127! /+!
3)/)*'0%)! /4)! .0O)6! .429)6! 2%3! +*0)%/2/0+%! +,! /4)! ;082%3.! 2*+&%3! /4)! 5+'9;)@! 0%! /)*'.! +,!
/4)!+9)%0%8.!2?20;2(;)!/+!.+;?)%/!'+;)5&;).<!!
!

!

"#^!

Normalized Change in Absorbance

0.0

-0.2

-0.4

-0.6

H2O
MeOH
MeCN
CH2Cl2

-0.8

715 ± 15 ps
963 ± 28 ps
985 ± 24 ps
1288 ± 52 ps

-1.0
0

500

1000

1500

2000

2500

3000

3500

Time (ps)

!

+.3,'&()4S*(T.138&(G#H&8&13%"(7&/#J(%'#/&2(0;(<+&=9$J?NA@B(.1(H#'.0,2(208H&1%2E(
=4)!?2*02/0+%.!0%!;0,)/0')!32/2!,+*!30,,)*)%/!.+;?)%/.!.4+1%!0%!D08&*)!#!*)9*).)%/!2!*2%8)!
+,! 30);)5/*05! 5+%./2%/.6! 9+;2*0/76! 2%3! 5+%/20%! (+/4! 9*+/05! 2%3! 29*+/05! .+;?)%/.<! S0%3.)7!
`2'&;2!0.!9)*,+*'0%8!52;5&;2/0+%.!/+!3)/)*'0%)!14)/4)*!/4)!2'+&%/!+,!255)..!/+!/4)!')/2;!
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Normalized Change in Absorbance

0.0

-0.2

-0.4

-0.6

H2O
MeOH

4.49 ± 0.21 ns

MeCN
CH2Cl2

-0.8

3.05 ± 0.12 ns
5.35 ± 0.32 ns
5.30 ± 0.31 ns

-1.0
0

2

4

6

8

Time (ns)
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