HAQ'‑BA

̲‑̲4,,

K‑:f

H2AQ

Scheme 2‑4‑2 Equilibria involving two‑step one‑electron transfer, formation of the hydrogen‑bonded complexes with benzoic acid (BA), and proton transfer in the hydrogen‑bonded complexes.

Table.2‑4‑3 Estimated hydrogen‑bonded complex formation _constant and electrochemical ^parameters giving^{the best} fit simulated

voltammograms illustrated in Fig.2‑4‑4.

Calculated Parameters of Redox Reaction

EO ^a cl ks

E10 _‑1.31

Ell ‑1.22

E12 _‑1.14

E20 _‑1.85

E21 _‑1.37

E22 ‑1.19

E31 _‑1.32

E32 _‑1.22

0.5 0.15

0.5 0.05

0.5 0.1

0.5 0.15

Calculated Parameters of Equilibrium Reaction

Keg ^a H kb

Kll 500 1.Ox107

K12 0.5 1.Ox107

K21 ^2.1x104 ^1.Ox107

K22 12 1.Ox107

K23 300 1.Ox107

K24 2.2x103 1.Ox107

K25 ²⁰ ^1.Ox107

2.Ox104 2.Ox107 4.7x102 8.5x105 3.33x104 4.63x103 5.1x105

K31 4Ax1012 1.Ox107 2.28x10‑6

K32 1Ax104 1.Ox107

K33 500 1.Ox107

K34 ¹⁵⁰ ^1.Ox107

K35 1.Ox103 1.Ox107

K36 1.Ox103 1.Ox107

6.98x102 2.00x104 6.54x104 9.86x103 1.Ox104

‑600 ‑1000 ‑1400 ‑1800 ‑2200 E/ mVvs. ^Fc/Fc+

Fig.2‑4‑4 Observed and simulated cyclic voltammograms of i.0

mmo1/L AQ ^{in the} absence and the presence of 0.25, 0.75, 2.50 mmol/L BA _at a scan rate of 0.7 V/s, The observed voltammograms denoted by

lines were recorded with ^a GC electrode (q)‑1 mm) ⁱⁿ ^MECN

containing 0.I mo1/L TPAP, and ^were background‑corrected. See experimental section in the ^text for details. The _parameters used ^to obtain the simulated voltammograms denoted by symbols ^are described in Table 2‑4‑3̲

7oT] I,>##&1#? 7T=@JE32jt&FS}*=xhhi>%j%19‑1 7oIE8=?U)Tb, #LE7o u771)VO)1fBk%H&7T=. ^7oD I‑>##jiFSbS)%3:maf=b, ^917oI ^, ^I tA ^fa

(). 5;If;I4</il)UIJ,i,‑,*E= 7il'DT‑>FSm))1),i:A 7:r))HA /3'e,‑&t/)ihb⁽⁾^, JilJL:ifZi(l'.ii‑Lttrl,‑i.‑L!V) (12)75,6(17)Tlj%Sn8. 5FyjiC(14), (15), (17)ri7oD ^I,>#&EiFS7?ZB8. ^7o[] ^h

>##1&0)7k/*13f5#ti7=*>(D‑) ⁱ L,Tf*iBi*8=3B&LTU)TU)i, 1&HjiFS%

J1.(i.fill^l^i:'t'}‑RL^Lla¹^/u.

AQ ⁺ ^HD

AQ‑HD ⁺ ^HD

AQ‑HD AQ‑(HD)2

HAG ⁺ ^HD

HAG‑HD

S AQ‑HD

S AQ‑(HD)2

S HAG ⁺ ^D‑

S HAG‑HD ⁺ ^D‑

S HAG‑HD

e Ii2AQ ⁺ ^D‑

KI K2 K3 K4 K5 K6

(12) (13) (14) (15) (16) (17)

'tM( a,iii;‑‑I̲TSZ)tI1<a).ill‑ili7:y+ ^{/ i} ti'T2lit‑^, /i(,i:.‑(lr;li‑L4<tilTl)jH3

cELRIS‑[rfI6/I‑‑̲I)kJiEE(Tt?i T ^{i i,‑}

EEC)ie(18)751⁶ (22)bS7ir$^{6 m8.}

[AQ‑HD] ⁼ ^K1 [AQ][HD]

[AQ‑(HD)2] ⁼ ^K2 [AQ‑HD] [HD] ⁼ ^KIK2 [AQ] [HD]2 [HAQ] ⁼ ^K3 [AQ‑HD] ⁼ ^Elk [AQ][HD]

[HAQ‑HD] ⁼ ^K4 [AQ‑(HD)2] ⁺ ^K5 [HAQ][HD]

= KIK2K4 [AQ] [HD]2 ⁺ ^KIK3K5 [AQ] [HD]2 [H2AQ] ⁼ ^K6 [HAQ‑HD]

= KIK2K4K6 [AQ] PD]2 ⁺ ^KIK3K5K6 [AQ] PD]2 S) >o)a(sWB%&% ¹ t18 tfiEO)ie(23)8='j%T= tbS>7?f8.

1 ⁼ [AQ] ⁺ [AQ‑HD] ⁺ [AQ‑(HD)2] ⁺ [HAQ] ⁺ [HAQ‑HD] ⁺ [H2AQ]

= [AQ](1 ⁺ K1[HD] ⁺ KIK2[HD]2 ⁺ KIK3[HD] ⁺ KIK2K4[HD]2+

KIK3K5 [HD]2 ⁺ ^KIK2K4K6 [HD]2 ⁺ ^KIK3K5K6 [IID]2)

I =TE.ie(24)kitlct ⁵ ⁸⁼ ^cL %&i18 ^i,

(18) (19) (20)

(21)

(22)

(23)

1 + K1[HD] ⁺ KIK2[IID]2 ⁺ KIK3[HD] ⁺ KIK2K4[IiD]2+ KIK2K4K5[HD]2= ^a (24)

'd/)(A,:;#.5‑‑(}5[[fI6^a)tlllrl)igti/J(jL:‑[lf;1j‑[1=f'T3‑)igJ3 A:V1S‑rLfl6!I:̲))ktJiiitiFx7:t7]‑{1^I i 7V7t i?3.

[AQ]

[AQ‑HD]

[AQ‑(HD)2] ^‑ [HAQ]

[HAQ‑HD] ^‑ [H 2AQ]

1/a

K1[HD] ^/a

KIK2 [HD] ^2/a KIK3[HD] ^/a

KIK2K4[HD]2/d KIK3K5[HD] ^2/a

KIK2K4K6 [HD] 2/a+ KIK3K5K6 [HD] ^2/a

(25) (26) (27) (28) (29) (30)

JZ2ltO)ie&Jn)T%7k*f#a%@Sj*0)ieLi7oT] ⁷ 7 1 )VO) 9h>9 ⁷ %1fBR ^L,, ^{Fig.2‑4‑5}

E=,J‑1‑LT=. It3(]ihLi5iHJ1/a^{J= j} ^(I. 7)(a,3;I)[;I)‑‑JrJI=j)STi)q!LIT=&b ^llTJr:I‑.̲u)+^/ ^> ⁱ i̲)5;I.fl67:r/fiJ)E L,f=. i L3^t= AQ ‑/)iYLilg([TL;I.'I:t=J=⁽⁾iEi)tg^{alYu i} [[,ltJT:(I./J(jL:‑(lI;(‑5‑[1W).;'T3‑1igE=LXl3)tL

VjlD ^I‑>!)ii$4U)^L ^I ⁱ¹^/a ^I ⁱ !JillI!Iq7I'iT.i?3.^{a: 7T=}^I a)Fq7h L17J(i;fit;lj‑‑(1<7blf̲T̲‑Lf:V)tiJtlri EPLX7?##L7T=F$0)Bi4k32jt&FS} ^*=x1'i> %fD8 ^I ^tbSh7?%8. 5T]ktih,^{Fig.2‑4‑4} ^TI

&1Ei&bS7>D ^‑ ^fintfE? 7T=7k#Rj;13fSj*bSuOO25 mo1/L3f# L7T=*B%, ^{Fig.2‑4‑5} ^{j= O} ,

/J(iL:‑[lJ,:ij.[1<tI,nTii:i)ilog(0.0025)⁼ _‑2.6 ^U)u!i. AQ ^)kLR1^1:1 S.[.H1(tiJ.TL;I‑.g{r7E;I.'I:E=cE⁽⁾iH}t^$ 41T AQ ^7=j‑> 9 ‑>I}))lily/I:.)'qT?37)i.llJ]]..1i̲E=7‑ltjT,>iJ( ¹ 5ii+i$1;‑))^LT‑E ⁱ ⁺ ^/

>9‑}*)VbS>fEBRgm8. $ 6 VLizS#) >9‑}*)V&V>%0) ^1:1 @Ej*tiiEB@qilkk j= Ot=#) >7=*>8=iZjtgm8bSh, RPqqf8=b5 ¹ 3}jlo)7oT] h>b5>##LT^

1 Ti>tj#) >&fEfiE18. ^3:7T=, ^7oT] ^I,>#&Lf=^1 ^TthDS) >0)BilEi&bS7L'T]‑

Tih7rlb8a)tL 3i#k8=ck ^O 7of] I,>j5i43%*#%9e5 ^7T=b, ^7oU ^I,>B,q#&FSbS>^tf3gtfI

?TU)8. L,blL,, 4>B10)‑>SIV‑‑>3 >7?tii2jtiBiB8=%BLTU)87T=b, ⁼⁰⁾ iBi2&#Wki*=1L,fab)? ^f=. ^5:7T=, 7oT] T,>#&L,7T=S) >bqg!Bo)&1Ei&i2&#

T. BllIE/I‑‑̲T)krnu)jff9:I‑iJil,i;iR!Ji/f7]2S';,.iJi),i;^{i L} ^I (J.:‑(̲L:1?JtJ+i7JiE^L. ^f ^JJ^I 7:Lh 7=r‑P1.RL 7T=. L,7T=bS>?T, SiB%L5a) ^BA

0)##tT,

^)Ro)A: ⁵ fj:*#Gf3:jiDSbS3gf7L,TU'8 ^b 0)t%k6m8.

AQ ⁺ BA.‑+AQ‑BA (hydrogen‑bond formation) AQ‑BA+ ^e ‑,AQ'‑‑BA (1stelectron transfer) AQ+e.‑AQ'‑ (1stelectrontransfer)

AQ'‑ ⁺ BA‑AQ'‑‑BA (hydrogen‑bond formation) AQ'‑‑BA‑HAQ' ^+BA‑ (protontransfer)

HAQ' ⁺ ^BA‑ HAG

‑BA (hydrogen‑bond formation) IIAQ' ⁺ e‑HAG‑ (2ndelectrontransfer)

HAG‑ ⁺ ^BA‑‑ HAQJ‑BA (hydrogen‑bond formation) HAQ' _‑BA+ ^e ^‑‑ HAG‑‑BA (2nd electron transfer) HAG‑‑BA‑ I12AQ ⁺ ^BA‑ (proton transfer)

(31) (32) (33) (34) (35) (36) (37) (38) (39) (40)

BA U)iJq;.i1/J(ii:;flI;.lj‑‑JrJ:jJ,L1^, AQ ^{3:T= tiIU)} ^BA a)/J(i!,i#['.‑‑{TS;L'fl4<(iJFE1.4iJL‑‑E[tE=^i:?

T3ZjtSm8 tRF$8= BA75167oT] I,>bS>#&L,, HAG 9‑}*)VbS>fEBkSm8. ^{$ 6}

E= HAG _{9 ‑>1))}^)L ^a:T=tifU) ^BA /)(i:;;I:L1:f}SLff[Wi,JFEli1)(:J[]i(I:I:E=J=?^I =J[Ti11^a a)iht

%5%UT H2AQ 7=*>75Sh4:BEgm8bS>, =0)tfb BAb'60)BPJ*0)7oT] T,>##

75S>G!=^O, H2AQ bS>fEBESm8. =0)j=5 8=iEj1#&t7oT] ^Tt>#&bS>#42L,TG!=

8 CPET } *=Xt'i>tL ^{# )} >xqO)g21Ei2jt} h=X>i> %4$1&LILla‑?0)fB)7?A

8 t%A ^6m8. #/ >9‑}h)V7=j‑>Bj=V>t=S) >7=*>0)7J(,*#.E%@Ej*

iL iE1##b) ⁶ ^7oT] ^I,>##^:g%PFEib7?G3%8jiFSO)f7?ZB ^O ^, ^%n%hmo)7oD ^h

>##igLii&(K23,K36)bShj(fh ^I ^tbS>, ^CPET } *=XL'i> 8=BU)Ta27flb8.

0 i

0.8

0.6

0.2

0 1

0.8

0.6

0.4

0.2

0 1

0.8

0.6

0.2

‑5 ‑4 ‑.3 ‑2 ‑I 0

log(BA]

‑5 ‑4 ‑3 ‑2 ‑1 0

log[BA]

‑5 ‑4 ‑3 ‑2 ‑1 0

log [BA]

Fig,2‑4‑5 Molar fraction of the various species formed by the association of AQ(up),AQ‑(under left)and AQ2‑(under right)^with ^BA ⁱⁿ

MeCN. The diagram was traced using the equilibrium ^constant listed in Table 2‑4‑3.

:1Jli7T̲fi;7/J(ji‑Ill;‑i‑)‑.[6‑(‑i‑(i‑T^E=^{J3 (1?a +} ^{) i U)})Ji‑fLfULjB..:‑f‑'i‑D[

‑#2#mlE%gho)#i&iZjtfE15E (E1/2)ⁱⁱ ^Koopman 0)k#KB;j)%Lijlo) ^LUMO IjT,)Vj=‑(.flu)^%jn)T,

F.E./2 ^‑ AGo‑ clu

‑AEs‑.1v (1)

T,Eei6T,fa. ^{I =T,} Aati@,qS,fE4qAO),SB}JfEI3E, ^AEs‑olv^ti 7=*>9‑}*)VO)f*

*E*DIjT‑)i,#‑t*Jr%5}jlo)i**EfDIjT‑)Vj=‑0)Z%iiLTU)8. ^3:f=, ^Ri7 ⁷ ⁹ j:A‑i&7:>1 eVNTb87T=b, I*)Vj=‑iB15E%eVifLk t18 ⁱ %%"P8q6E7?b8.

B2E=, (1) ice)LB%klq18@< 0)mRhEBtbS>b ^O ^, %j11b3Ei+5fb) 64$6m8LUMO

I ‑+,)L‑i=‑tiiS;‑)‑i;I.Ti(i(I:a)1,Tip)7:yJ=<.ffaryJT?a^I t7P11.tft141TL ^l^/a. L7), L, iH)i‑'nl iJltiLUMO^U)I.Ti‑l'‑JITJ‑^E=f[Tj1?a)1&FI!Ttb ^yJ= S)7h7ha‑) t3Tt. /ilJk1/a ⁷ ^=j‑ ⁱ ^I)

‑>th⁾ⁱ U)k'‑'JA:(E(I:Pi‑‑^L,ⁱl3;:3?').i7:yJ2(.1?3.^{L f=/)ih?}^T. i;LUFJ)uJJHil^B'.)tT/a /)(i,i#.I,‑‑(TU) I;;u‑ntfLY‑):‑uruf=SbE=tLi['Ill&(1)*J7)ⁱIT,t'j‑I/S;fT/a^I ⁱ ti1,‑Sam)T19/3. ^I ^=7?, iu‑LJr‑Ti [i /)irCh.'f‑!n'.J7Ti1'‑i'llT‑I^I⁾⁾^T. A ^/a I i ^fI‑,t'3.I..i:i:^L. ^I,jJtiliH}tJiEI;I;i:J'^J32ihtJ.=BI;.I:^E=*fT ^/a /)(i;

;I:if...i‑TU)iUu^nt7:r,ii'6.;A)1i717Ji,i.(i^E=8i, I4 1f14ⁱ^'a'1iliFlre.gil'kT^/u ⁷ ^I ^A‑ⁱ ‑)‑>1‑A^)L^U) j _‑)1J]

)v%iE (SOMO) *#2i&TfEBE18 9x1 7=*>0)HOMO8=}+185iLaB%%*L&L,I

%iEiELJ2R18 ietfbS>4=^i;^a.

)JLf.Julia.:‑f.̲BT^A/I^J‑‑_‑j^E=zBT= ^(). rwTJL:̲a)J[Ti1'‑1Ji‑fig.frlt'Lril‑)iEJ=^< =1i^L ^, 71,7.i‑T.‑iT[^j ⁷¹ ^1,^a) IRU)iE1#&iJLiB&B3IXP%Jn)f=. 2STfBtiq&ti6‑31++G(d,p) &jn)Ti83S &iaiBLE

L. + / >iX)tI6)iLRIIU)7J(iL:‑#.Ii{}S.l.f(1<U).fJLiB‑I‑jT.)L#‑ ^fly^;J1‑^L ^, /)(A,i#.I.‑‑I̲}5;Lit[〜r5)).k

E=ct7JTULiCI ‑+,)L‑i=‑,Af[E7h_LL/J(i!.i3:[Ii‑{3.a),;'juLILa.i‑JYi.;‑rli7L f=. ‑1=5hiLIULihl‑I‑‑^i‑1:Tli.;‑[.‑^*

a)rLtt)lu.3IEV)f=i5,AQJ= ⁽⁾i̲'.)}Lf̲:[tj)i/JlS^<. fJl?jlifTMJ‑i‑,'J;Jr:I:.a)(..galf=^ > 1j+ ^{/ i.}

(BQ)%f{JB ^L7=.

Fig.2‑5‑1 tiBQbS>7k*f1#Sj*Tb8 ^{i 9 )} ‑)Vt1:2Bj=V1:4@Si*, ^7I/ ^‑)Vt I:1BJ=V11:2@E1S, #JBLS@ i 1:1BckV11:2@Sj*%Jr3BE L7T=F$0)%#iE4XPhq8=B i18ia i*1EtB3S%/j% ^L,f=. ^{5:7T=, %0)} t%a)7k/ii5jS#E%0)&S ^%Table ^{2‑5‑28=j%} ^L,7T=.7kiFejS#E 0 ^a)^{Li a} (i/)(i:,::()I;I‑}11<V)q21:tliEiJihT'::,‑ⁱ^l^(=d.^thlfiI< ^, a:f=BQ/)ih.‑Li(',.i7:rJ.I;J.;LR17JJIt11!7^< ^{tj: ()}^, /I(jig:,Iit:T!Jtt.]i;.^< ^fI^/3 ^I ⁱ iJil‑.!I!IRJ7II.Ttf^/3. Fig.2‑5‑3tii:j3:J[JLiBtI‑+,)L‑i=‑ fLY[t47T{L f= b a) ve.zB^/3. BQ Lu‑Ji‑a)^r77]ftTi̲U)[IULjB^7:yJr:!‑tikret&.'i‑V1.^‑I‑4^Ii).9LU)!tJL3ati/J(ji:;(lL;‑I)‑‑[1<a: f= ti:L‑

o)1thO)BQEb*0)%3fT,, %3iifO)LUMO, ^SOMO,

HOMOO)%3fljT,)V*‑bBB

L,7T=. 3:7T=, Table 2‑5‑48=7j(*f#E%@Ej*Jr3Bk8=J=? T#ilESn8A'BthljT‑)Vj=‑&

ASCFt L,Tj% L,f=. ASCFtiBQ7k/ii%j;#E%@S#0)SCFb1 ⁶ BQBckV17j(/*13fSi*bS>*

5u).T().:(I‑:TYui 5 a)SCF*LY ,‑3[ⁱ)f=IEi7?.

/fllU)fuu)U(iⁱ

ltia"i:Jji:[EU)51;ul1!!Ji)(iⁱ^).

'J:: ^::

JJJ

JJ /JL ^J

Bq‑ME4

PJ.I

^IJ

I:,

+ i‑4J/Jt‑

Ji‑‑i,

BQ‑BA

+ JJ}

Jri‑J

+ J.

}JJJJ }JJJ}

BQ'‑.PH:

} J

I‑Jt}

:J:

+ J

J4 _J +

} I

BQl‑‑pH

I:.J'.:JJ

+ ^J 0

:::

JJ JJ

i', _.)

.,S a.I.

Bq,ME2 i

･jJ::J'J

)

}

Bq‑PH2

J‑: ^:8J

J..,::.J JJ:J,

,9J,

,i.

8Q'

‑

‑ME4

} v‑4.

}JJ J+

H8Q ^I. ^tu

a) Chat.ge ^:⁰ I }JJJJ

}J.JJ

:I:I:

+ .+

JJ:;::

Bq.PH

b) Char.a,qe^:_‑I

J}J

+ JJJJJ J.JIJ}

}:

BQy‑‑ME2

}JJJJ

)i‑:‑a‑J

JL‑,

HBQ +

J +

} }

.‑i ?

J J

}‑1J + BQl‑.I)A +

J‑. J.1J

}JJIJJ +

c) Charge ^:^‑2

+ J.J.J

J‑JJ‑

BQ:I

JJi_JJ.

J.JI.J JJJIJJ +

JS.

J.4.}

Ji{

^:i..

JJJJJ

JJ.. A‑}

+ +A J.J.J

JJI.JJ +

J‑J.rlJ

JI +

44JJ 44J‑J

+.J.

I.‑44J

8Q2‑,ME2 BQ2‑.ME. BQ'‑.Pt{ Bq2‑.pH:

} JJI JJI‑

JJfJ:.

+J JJJJ}

JJ.JJ +

8Q2‑‑BA

J+

J.JJIJ

JJJ‑JJ +

HBQ‑

JJ JJ

JJ JJ J+

+J ^‑..

+I +

t7ESQA‑^BA ^H..BQ

Fig.2‑5‑1 Optimized _structures of BQ and the hydrogen‑bonded complexes with ME, PH and BA for neutral BQ (a),^the BQ radical anion O)),and the BQ dianion (c), calculated with the B3LYP/6‑31++(a,p) method. The bond distances lists in Table

2‑5‑2.

Table2‑5‑2 The bond distance in the optimized ^structures of the hydrogen‑bonded complexes of BQ.

charge:0 BQ BQ‑ME2 BQ‑ME4 BQ‑PH BQ‑PH2 BQ‑BA

cl‑o2 1.227 1.235 1.238 1.234 1.233 1.235

o2‑H3 1.975 2.008 1.885 1.898 1.812

H3‑o4 o.973 0.971 0.977 0.977 0.987

charge:‑1 BQ'‑ BQl‑‑ME2BQ‑‑‑ME4 BQ'‑‑PH BQ'‑‑PI{2 BQ'‑‑BA HBQ. I{BQ'‑BA

c1‑o2 1.272

o2‑H3 H3‑o4

1.279 1.285 1.288 1.282 1.318 1.357 1.266

1.720 1.772 1.538 1.591 1.076 0.968 1.713

0.993 0.986 1.026 1.013 1AO1 0.997

charge:‑2 BQ2‑ BQ2‑‑ME2BQ2‑‑ME4 BQ2‑‑pH BQ2‑‑pH2 BQ2‑‑BA HBQL HBQ‑‑BA II2BQ

c1‑o2 1.316 1.332 1.342 1.385 1.361 1.390 1.412 1.347 1.377

o2‑I13 1A10 1.560 0.992 1.015 0.982 0.965 1.020 0.966

l{3‑o4 1.079 1.026 1.794 1.604 1.883 1.569

All values ^were described ih^A unit.

(a)

O))

(kJ 1110l.1)

C _〜

⁺

0 Jr̲ 5iE

‑400

(kJ mo1'l)

I‑?00

･iOO

･600

:E23...EO...LJZE...,L2iO...tEZn...Lie

! ⁺

HOMO HOHO

....‑.ll̲

H OL(O

〜

･'m

''''TUEd

!TTT7T:...l'

BQ ^ZiQ‑1ZE ^I ^a Q‑1(E4 ^a q‑PH ^aQ‑PH= B Q‑BA

LET....,

〜

LuhSL.""Li2aii...‑...̲...

e2ZZ2̲J

HOMO ^‑I...

〜 4〜

d3?

‑ J‑

qLW

undo LT!E LTt6f6l...̲

1 I

〜.B2E9...S9Zia...i‑.‑‑.S9q

･.P...̲^qi2ALn

LE2E2_.I^I...

I‑

''..

I I

't.:'iS2Zi9I

''...

SOZW

HT='''"''';

I)Qr‑ Bqll.1lE2 BQl‑,1(E‑ Bql‑‑pH Zlq'‑.PH2 J3Q".ZiA HZ3q' HBq'‑tin

(C)

BQJ‑ BQ=‑‑hE: Bq2‑‑LIE. Bq:‑.PH ZIQ>‑PH2 Zlq=‑.BA HZlq‑ HZ)q‑‑DA H?q

Fig,2‑5‑3 Energy levels and illustrations of molecular orbitals for BQ and the hydrogen‑bonded complexes in neutral BQ (a),the BQ radical O)),and the BQ ^dianion ^(c),calculated with the B3L'YP/6‑31++G(d,p) method.

Table ^2‑5‑4 Stabilization _energy (USCF) for the hydrogen‑bonded

complexes formation, and the energy levels of LUMO, SOMO and HOMO of

BQ the hydrogen‑bonded complexes.

charge:0 BQ BQ‑ME2 BQ‑ME4 BQ‑PH BQ‑PH2 BQ‑BA

ASCF LtJMO

‑381

HOMO ‑745

̲49 ‑91 ‑28 ‑54 ‑37

‑404 ‑418 ^‑414 ‑443 ‑400

‑716 ‑725 ‑581 ‑589 ‑701

charge:‑1 BQ'‑ BQ'‑‑ME2BQ'‑‑ME4 BQ'‑‑PH BQ'‑‑PH2 BQ'‑‑BA I{BQ' HBQ'‑BA

ASCF

LUMO ²85

SOMO _‑41

HOMO ‑230

̲112 ‑204 ‑88 ‑165 ‑87 70 ²⁵

217 ¹⁹⁸ 181 ¹⁶⁶ 169 _‑111 ‑128

‑133 ‑206 ‑127 ‑195 ‑201 ‑578 ‑605

‑332 ‑404 ‑294 ‑325 ‑332 ‑694 ‑677

charge:‑2 BQ2‑ BQ2‑‑ME2BQ2‑‑ME4 BQ2‑‑pH BQ2‑‑pH2 BQ2‑‑BA HBQ‑ I{BQ‑‑BA H2BQ

ASCF

LUMO 560

HOMO 463

‑231 ‑407 ‑252 ‑437 ‑284 ‑420 ‑568 ‑462

430 ⁴⁰⁸ 370 340 334 234 172

‑60

309 222 251 ⁵¹ 227 _‑5 _‑212 ‑562

All values ^were described in kJ mo1‑1 unit.

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jB Lf=)1Y*= }jlJI.y 9faiEj1#&A75S'#jiSmTU)8. ^L,75)L,, =m6tilgmb I,G‑fl3P)yFruiV)A+uTIi^E=_cE? ^T J;i‑fi‑/JJLfi ^U)i3ifni]i^fly;I;‑lrTJtP^{L,. I} a)'[ld‑ffSJ3‑))7:r^j ^> I‑^u

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k'‑CtlBli[Ei2jtJ[:(:̲7:r‑,1tT^I i 7hLIJ.‑E'x‑([EJ1;.I‑'U))Jiu!J1',TliLElilfiry)f';r^{i L TJIJ}ⁱ^l^t13^{1?a 7} ^I

D i=> fLYAikf.iTfiL,T=f9‑lJiJ[31]. 7nL ⁷ J{ T)i A+uF('li'iiib5i^*JIJ ⁱITytJ,‑‑ii'jifSm)tpHU)ri!:‑1Lb$1 7:r(Jr.J9uLL T=f'/‑I)[32] fTtf.:A^k 7f.A/a. ‑1LT;'fretL⁺ ^{/ i} I);:ill:7Ti‑I.li11'9i̲[‑̲(=RqJii:[ELiT=A2zB[li I.‑E4‑['9i7:r[1‑:‑.'iil^L. ^Jlt^{1 A‑}ⁱ ^{* j1 1.y} ⁹ fiEJ,TLh'‑iSj3))tj=))LjRU)1‑lVi5jt'=y,ilt#.JrTE;‑l'‑iSP)yFftli

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f=Lgf;7][r.‑E1.̲r'')iU)[1I.'b‑il*J1‑:r'b!^{L T=.} i/ilW1‑:‑r'b5^{L T=}f+uTl;I.‑G1‑()i^tL 1? i fj‑‑)L /)S11&ri‑‑T/JTJ̲I:̲

fri‑*LYS.u)H^{L,f= S̲)}^U)re, ^j=j‑‑)L fr:.#.A^{L T=S} ^/ >.‑i,1;I:.̲ffl4<^flylr[‑E4L!gijinT‑E=^FITL13:ILijLMEⁱⁱⁱ LifBS(SAM)i L,TJr3BESifiT=. ^I 0)a: 5 8=fj‑‑)VO)#J[%&*rJJB LT#) >i75**j*

i:4;iE4qB=4TgeSSiff=qfJti@ ^< ^, iEf##8=1B L,TO)%E%i3EbTU)a [33‑36].

I ^a)

‑‑T‑‑iLtifj‑‑)L^)i.3r,=rf.IJ‑:?/)Ji‑j'‑7Ji^(t>̲ⁱ 1!Jl:blM'JE=#..I..I/ULT 7JfJl:̲Tf *JJ‑i:)I)L ^, 4L!)‑:fMj:,lBfi Gfi‑^+r LEIig‑i ^ifT1.r& ij‑‑ry)f'i^fur^'LI;!jliJ,{tfitI/ir]1^l=^J.‑E1‑BjiE‑t'1:i7:yu.iili‑I^/a 7tli‑7f+i; hA^E=_lt::)‑n&.:1ii:^, lL::)‑r'5nr'T]JrJf:̲u}tLiifji‑jlJJ.lli7=y)r‑iT)kT^/3 ^I ⁱ ^/)ill:I^‑Lf^/u ^I ⁱ 7Jq‑!J‑:‑k7?^A ^/a. ^I ^U) ^{i i} I+1&^yi‑‑rnfi‑⁽ⁱ 7)VS)V53j&FB ^U)⁸ ^I tbS>@ ^< ^, SAMO)I)RjtBgf3:XR9,f]f8iStijlt L,T7)V#)V$1jFpq

a)van der Waalsj)t=j=? Tijtb ^6mTU)8. ‑A28=, @,[J533SBtyeg%BO)van^der ^Waals

l'‑‑ff̲J3^J=7JtTir^;ITL:ⁱ fhji/ⁱ⁹ ^S ^‑ 9 ^‑ a)R'Tl!)ii,‑3%13LE= fj:?3 t5t1. :LtrJjLflJ.lI!u)1‑Iflri3U)ihrl3ll^i L TL ¹< 1tl'i[6J7Ji35/a.fU)f=&5. ‑I;]'1r'{JE=ti7)LS)LfiliU)l7{j,;.‑2&/Jilb/A‑1)igtJJ‑̲4;i⁾

lii‑{Tt=.JA!Jii:,I[:,i'i?.:lig,T[::;Ber['fJi:I‑:a)SAM/)sir.il)kSa^I?3. ^a:f=. ^I U)T‑‑fiiiil[:.uJi‑I‑JJl;Jib

JFEIL!gLL(=[.I,lJjE1?a^I i 7PIT.i, 1‑i ‑+,)Li';u!1tL(I?ⁱltd)fi)FLJ)VIttTIT[L.'1‑)i;^Lu,i:[nWliturf:J':7 TU)8 [37].

I =7?iL 9,10‑7> f,9S/ >%@%4:jgRi58=B]klES;&TJn)f=. ^{Fig.3‑1‑1k} AQ@eRiiE4qAO)1fA8=jP)f=N‑(2‑})Vh7o I,I91)V)‑7> I, 9S) >‑2‑i 9 >1 ^{i >}

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8 =t75S>TIf7T=. %BEL7T=N‑(2‑})Vh7ohlf)V)‑7> h9S) >‑2‑}9>1 i >0)

･lB!EfL,'bqmmouLtfa8 ck5 8=7‑E I,^I I, T))V8=i*# ^L, ^7)VS j‑Tiii5&mLg L,7T=4>

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*J1=f9uiT=. =U)J[TL;1i'9iTILI.Tiq!jiTntAQ7:r7)L+)LS;L'it ¹ ⁱ >7:.!A[lhri^LTJ3 ^(). ⁷

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J,Ti(i(reti7,‑̲'&'‑JJtveb^(). SAM7V7;dJl^i.1/a^T=B. SluI7h"A!J/i:E=IhlJ=aⁱ^/a _‑1700 _mVj: 7:I a) ‑'rr〜dP[ireiluJjiI^{A/(‑]‑‑‑?}^{T=. a:f=.} SAMJ.TJll̲rgi7:r)H^i.)T=jf.[,FEY.t.iAlgfyTia a lT= 5}+E= cE⁽⁾I a)4‑!J‑:.I:Iitil]U3:⁽⁾ [38]^, JTGitiE(atJ.TilL[gi(Ir.I‑,‑1JiiitfE^a nf=3:jijltf'{(;^i:ii)ft]r>q7:rf!J‑:?f=}5, Jji:rT7̲:n'J[nJ,'[!f)i^S)^ITTfJtE^Pet^35?a.

‑̲L:::̲L:‑

CH20H

2^‑hydro _xymethyl anthraquino ^ne

H2N‑

‑ H

P Cr‑ Cl

Pyridhh chloro chronute

C yste amine

‑̲L:̲‑:̲L:‑

Anthraquino ne‑ 2^‑aldehyd^e

:I:::I‑L

N〜

CHO

N ^‑(2^‑^mere aptomedly1)^‑anthraquino ^ne ^‑2^‑methane hhe

Fig.3‑1‑1 Synthesis pathway of the N‑(2‑mercaptoethy1)‑

anthraquinone‑2‑methaneimine from 2‑hydroxymethyl anthraquinone.

'LJli=fiT)‑⁷ ^> I‑j S / > AigBTTiJ[li1‑[IJiU))i(A,,:‑3:.Li‑{}),i:A,==.1J[:̲

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9 ‑}*)V%i*tH18 ^I ^tbSTT%f=. ^I 0)WklESn7T=AQO)i2jti&t&1bi&0) tf‑9%

L5Eti%mf>m‑1410mV, ‑1242mV&j%L,, tic‑90gti168 mV7?ZB?7T=. if=#=*

7?177 f=)1>)V9 7r10)Sp5*7?tL 32jti& t@Jbi&0) ^tto‑ ⁹ iElkti%nf>n‑1357 _mVt

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a) i i t=lt<),i:.^i̲t;.T1:jJi.'u'‑‑.i^l^I i /Ji'T(n#1^{a a}¹^f=. ^I ³¹tiAQ/)ihJrTd1‑rgLL^t=_r'::;i.*.'13i:^t=Tr[.lJjt[t:ⁱ nT=f=b, 3}fe)3d;%8EjJbVa< ^fa O , iEf#&bS>ST]FRSn8f=b t*A ^6n7T=.

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̲[‑̲U)AQ/)i,T1‑TCVV) }r$4iJ)^fr Fig.3‑2‑1‑Fig.3‑2‑12kj% L,7T=.Fig.3‑2‑1tiNN'‑‑}} j=)VR#Fi, Fig.3‑2‑2ti7 I ) ^‑ )i,, Fig.3‑2‑3ti}9=)Vp‑t= ^U fih#‑>Ji>')i‑ T,, Fig.3‑2‑4tip‑t= TihT]S‑>7t Tt7

I) ^>, Fig.3‑2‑5tip:>7) 7I)‑)V, Fig.3‑2‑6tip‑I I,D7I)‑)V, Fig.3‑2‑7 tip‑}}j=)V7S )#B,S@, Fig.3‑2‑8tiW@, Fig.3‑2‑9tip‑7=X@, ^{Fig.3‑2‑10} tip‑ I,)V1 )V&, Fig.3‑2‑11ti#BtS@, Fig.3‑2‑12tip‑7 i ) #B,S&&i*i&* 8=iS bn L,f= t50)@eSiEf@to)Ago)CVT'ZB8. ^=m ⁶ a)##1E%4ho)pK%Table ^3‑2‑13

f='Jl‑Lf=. _‑)1f f)LTF1{ji:‑*J;::Hlf=/I(iL:‑(!f;i‑j‑I6E=^lf;‑3dLT, i'T{I)igu)Jill','))IH=fl'‑‑‑3^I. AQ a)@1EiZjti&bShjf‑}j1,I ^7F;)7

T,18tVO)#4EbS>‑aEhb

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i}‑‑(〜)Wigtn;JFE1[)iI‑̲a)AQU)I.TL;+i3P)^E= Ij‑iL7J;ITS‑I;.lT1.‑iti,jlg <. 'j1‑iC^U)TfT)'grf:̲7:rIT'?^7T=IF

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%JT3BEL,t=< ^< fa?T=f=bt%k6n8. ^{3:7T=, Fhx} I,Life)7k#F,jS#E%i}1 ^hTb8

‑OH%‑OCH38=fE#;,tL,f=7=')‑)V#,&##Eiff= ^tf ktL 7k/*#E%SE&9e? ^f=7=

bCVO)*&8=2elE75Vgb1?f= ^I t&6@EJ%hLf=. ⁼⁰⁾ ^I ^{tb) 6,} iEi@̲EO)Ago)@1E32 }tJi I,i:^E=^S)/I(j!,::flI;‑i)‑.(〜)ih/J(i!,‑:.‑A,li‑(T7;y.)i^L ^I ,r;13?g.i^fly^Jk({t ^I ⁱ^l?a ^I ⁱ 7:r1);Ii‑IT:̲Tt^{i f=.}

‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc'

Fig.3‑2‑1 Cyclic voltammograms of the AQ‑SAM electrode(q)=1.6 mm)

in the presence of various concentrations of NN'‑dimethylurea at ^a ^scan rate of 0.1 V/s.

‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc'

Fig.3‑2‑2 Cyclic voltammograms of the AQ‑SAM electrode(q)=1.6 mm)

in the _presence of various concentrations of phenol ^at ^a ^scan rate of 0.i V/s.

A a

0 1

〜

‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc'

Fig.3‑2‑3 Cyclic voltammograms of the AQ‑SAM electrode(q)=1.6 mm)

in the presence of various concentrations of methyl p‑hydroxybenzoate ^at

a scan rate ofO.1 V/s.

1 o

tttt

〜

‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc+

Fig.3‑2‑4 Cyclic voltammograms of the AQ‑SAM electrode(q)=1.6 mm)

in the _presence of various concentrations of p‑hydroxyacetophenon ^at ^a

scan rate of 0.1 V/s.

A ²

‑2

‑4

‑6

‑800 ‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc'

Fig.3‑2‑5 Cyclic voltammograms of the AQ‑SjM electrode(q)=1.6 mm)

in the presence of various concentrations ofp‑cyanophenol ^at ^a ^scan ^rate ofO.1 V/s.

<12 a

1 8

〜

‑4

‑800 ‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc'

Fig.3‑2‑6 Cyclic voltammograms of the AQ‑SAM electrode(q)=1.6 mm)

in the presence of various concentrations of p‑nitrophenol ^at ^a ^scan ^rate ofO.1 V/s.

‑800 ‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc'

Fig.3‑2‑7 Cyclic voltammograms of the AQ‑SAM electrode(q)=1.6 mm)

in the _presence of various concentrations of p‑dimethylaminobenozic acid at ^a scanrate ofO.1 V/s.

A q2

tttt

‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc'

Fig.3‑2‑8 Cyclic voltammograms of the AQ‑SAM electrode(q)=1.6 mm)

in the _presence of various concentrations of acetic acid ^at ^a ^scan ^rate of 0.1V/s.

A ²

I ^o

‑2

‑4

‑6

‑600 ‑800 ‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc'

Fig.3‑2‑9 Cyclic voltammograms of the AQ‑SAM electrode(q)=1.6 mm)

in the presence of various concentrations ofp‑anisic acid ^at ^a ^scan ^rate of 0.1V/s.

‑800 ‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc+

Fig.3‑2‑10 Cyclic voltammograms of the AQ‑SjM electrode(q)=1.6 mm) ^{in the} ^presence ^{of various} concentrations ofp‑toluic acid ^at ^a ^scan rate of 0.1 V/s.

a 2

tttt

〜

‑800 ‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc'

Fig.3‑2‑ll Cyclic voltammograms of the AQ‑SAM electrode(q)=1.6 mm)

in the _presence of various concentrations ofbenzoic acid ^at ^a ^scan ^rate of 0.1V/s.

‑800 ‑1000 ‑1200 ‑1400 ‑1600

E/ mV ^vs. Fc/Fc+

Fig.3‑2‑12 Cyclic voltammograms of the AQ‑SAM electrode(q)=1.6 mm) ^{in the} ^presence ^{of various} concentrations ofp‑aminobenzoic acid ^at

a scan rate ofO.1 V/s.

Talble 3‑2‑13 pK ^Values of hydrogen donors estimated by calculation

program, Advanced Chemistry Development (ACD/Labs) ^Software

Vll.02 (1994‑2010 ACD/Labs).

compound pKa

NN'‑ dimethylure a

phenol

methyl ^p ‑hydroxybenzoate p ‑hydroxyacetophenon p ‑cyanophenol p ‑nitrophenol

p ‑dimethylaminobenozic acid p ‑aminobenzoic acid

acetic acid p ‑anisic acid p ‑toluic acid benzoic acid

a)^Refereced ^from ^SciFinder.

14.57 ⁱ OA6 9.86 ⁱ 0.13 8.31 ⁱ 0.13 8.12 ⁱ 0.13 7.79 ⁱ 0.13 7.23 ⁱ 0.13 4.91 ^j= 0.10 4.86 ⁱ 0.10 4.79 ⁱ 0.10 4.47 ⁱ 0.10 4.37 ⁱ 0.10 4.20 ⁱ 0.10

Fig.3‑2‑1 Fig.3‑2‑2 Fig.3‑2‑3 Fig.3‑2‑4 Fig.3‑2‑5 Fig.3‑2‑6 Fig.3‑2‑7 Fig.3‑2‑12 Fig.3‑2‑8 Fig.3‑2‑9 Fig.3‑2‑10 Fig.3‑2‑ll

‑i, ^FAX I,5}jltL,Tp‑I ^I,tj7I/‑)V (NP) %jf#Siff=t%, AQa)‑*tE jlB 0)&4E32jti&0)7F‑}jlJI ^7L'‑>7 ^H=bDk, ^{$ 6} VL=iEjlB 0)32jt&FSt=G3BIT8

i ‑.t'j‑iLL3a1/pi3}tiB7V+aiillJJg a lT=. L 7h b. ^I J)iEi‑}‑L;iTIU)i3j‑tJ,TiitiEtiNPU)flT3‑]igu)lr.l'.I))fl E=I1'‑‑^‑? TP.l'.T)(^L. zyFE‑I‑iSdf))+r,7‑;T^{* 5:A I} ^I‑ ‑> ^a >J.TL;it)iE!)i5E/I‑‑̲L T=tlf(::i!TJJ5 a lf=.

I a)} 5:hj I‑‑> 3 >iEf}fLtL AQ4?ge6iEig@&BfB] ^{L,f= i} %0)b&iP,[J18 ^I tbST%f=

FIB, iEr@̲La)AQbS}j=hJI ^I‑‑> ³ >%i}fL8=j(i ^< SSL,TU)8 ^I tbShLib)8. ⁼⁰⁾

I tfJ, LIJ[TLH‑I̲g‑LI‑̲U)AQ/)ihj=t^{T) 7‑} ⁱ LT(Di)uf. NP!JitiE;‑)‑L1/u^I ^i(=cE‑3 ^T f$1 ^I

‑‑> ³ >%f}fLbi>5efELTU)8 i?ifUIL,f=. ^L,75)L,, CVO)#EBtA) 6T,tL NPb3h32jtg mTU)a I t&JEEFBT8 ^I tbS7?%f3:i)FIB, NPbS>32itSm8 ^I ^t8=j= OfEBRgm8 NP7=*>9 ‑}*)V%i*HT8UVXJ<9 I,)VO)iFgJk%aiE*7T=.

;J3I L^u1‑I,‑B+f3DUJ^U)5jiytJli.1'r1'.Ji!1JJJjii]

‑A28=#*IE%4ha)7=*>9 ‑}*)LO)XJ<9 f,)LtL iSj*1k%%t=tb<T&i&&

quH=#!J‑:iTxrl'.Jfiir7)i)(i7:r>Jt1. ^I ⁴¹(i/:]‑.(6[E(Jhrz)U)lil(ltJiE!J.JLjaL(LUMO)^U)‑‑JrTh'‑[LTJ‑A^E=

ck? T!r‑‑̲lJ+eT/a‑I,TL;‑f[lT‑‑[J‑.rUtiB(SOMO)!Ji,^HOMOcE ⁽⁾ⁱ⁾^I pT,)L#‑itLi[u)i1[L;':)‑ⁱ^IT=i5

7?b8. L,f=b5h?T, fEBRSn87=*>9‑}h)VbS>#kt=#if18*B%ktL 5iiX

I.E/xtLEJl:(I‑'n'J‑T‑‑fi:t=_cE? ^I, ^I ^a)^fJiJ)k7Ti‑Lil(I.i.i‑LJ.T?3^I i 7Ptvet‑i?a.

ilJ[J‑ilnTtAQAiXBr‑lJ‑I,TI1‑['gi^7:y)TH^l^/a ⁱ NP/)itiht ^{g a}¹^T=^I ⁱ !JS1(r::itlI!Ja a tT=. NP'W)JrTd'‑I‑iSP) felt‑I(f!.i,i).I/a^T=&5 ^t=UV7l ^J< ^{9 I‑})Li17JrJj:^flyiJ‑‑? T=. i)fEYJ!(i100mcshU)

̲1>̲ll.JL1'.‑n'['gi

*JI) ⁱ^l, i')T)IL^u:I)‑(tJ]I‑.:At=AQ ^r'rL3:ILiJ&(E

‑iii)Ji‑7‑1Jtl‑i^{i L} ^T (3ffTIiT^/a ^I ⁱ T.AQ dLuTIi1>gltlJ.Til'.'gky(1;;bu ^T=.

4fA L,f=@#RfElqBiFig.3‑3‑1kj%1j= ⁵ 8=21&o)figs‑E)V7?39e*, t)i,0)‑F%B%NPiS JuHJiEIRFtI.i',{riitI/2^E=7ti1.T^I ⁱ ^t=_ck ^(). ^IEq['tlI7JAB:lli^(i'!^furI.u)^I) L,TJL‑Elih..''.:[:^E=J.liPJr'IL.iJifit(,2fLY.iI.'[[.]‑.f=L f=.

JFti'[RJ!J':iJiiit[/2^t=^{ti rT;‑]}I‑:furkf 4'['Q‑(.Ti1;g7̲J3^J=LRt,jfH[).EiJiE1'LT)7̲7i‑1.T.‑A L. I f ^{1 I‑} _‑> _̲q ⁱ J.TiilM)iBlillJJ a a liT=‑1140‑‑1520 nlVreJjEJiE(Ill:JG'Ig,'II‑7:rf:J‑‑i^1. ̲‑j2,1:(t1.:ff:I̲1r/:a)

7l 〜 9 )‑)L/JJi4‑rr*/(J‑‑i^1, /(i)I:

6m7=XJi9 I,)V&Fig.3‑3‑2t=j%L7T=. %0)#EB!, %13E&EPbHT8 t=a:U), m400 ^nm a)xJi9 HVb5Tfmn ^L,, m310 _nmO)X<9 I‑)VbS>b6%'j>^L,f=. i5#NPO)i2jti15Etim

‑1950 mVT, NPtin310 nm8=, NP7=j‑> 9 ‑}h)V8im400 nm8=R2k4R45@j(&j% ^L,,

‑1=jiEj(F!1=J‑3ⁱ^I^T ⁱ⁾JFE‑("‑i^*J:‑IJ))H^L ^I ⁱ^ltd:ⁱINPJ[‑MJ,'lJliJifII;iTliNPU)i(J3¹⁰ nm/)itBiillJJ^{i 4}^1.

NP7=*>9 ‑}h)LO)n400 nmi=Xj<9 I,)Vti%iF,I)Smfa75)? 7T=. L,75)L, NPO)3Z jtfEL3E(A‑1950 mV)j= ^{O b/]tg} U)3ZjtiElk(‑1140‑‑1520 mV)Te, ^NP7=*>9 ^‑}h )LO)m400 nmO)XJ<9 I,)Vb3>i*EBSm7T=. a:7T=, XJi9 T,)V#L5tL %1k&EPbDT8 8=#U), NPO)a‑310 nmbS>bR/ILL,, NP7=j‑>9‑}*)Va)a‑400 nmbS7Bj(L,f=. ^I

0) I t75) 6AQ4pge6iEf@%Jn)8 ^I ^tkJ=?T, iB#T>iiNPbS>32jtgn8 ^I ^tbVaU) iBl)‑LJ,Ti'f1'I:re.NP7Phi3}tg a lT= ^I i 7Pt6&i‑,B5^{4 1{=.}

detector

Fig.3‑3‑1 An optically transparent thin layer electrochemical (OTTLE)

cell with ^a transparent gold minigrid electrode sandwiched ^two ^quartz plates.

250 300 350 400 ⁴⁵⁰ ⁵⁰⁰

wave length (nm)

Fig.3‑3‑2 Spectral change with electrolysis of AQ‑SAM gold electrode

in the presence of 0.001 mouL p‑nitropheno1. The UV _spectra ^were

observed ^at applied potentials of ^every 20 mV from

‑1140 ^to 1520 nN

ll I‑̲U);I:.J.:‑llUJlt3. 'FElq!!J,t3NP^U)J.Tdllu)I!t.qo:(H=J3ⁱITJ,‑E1'.i)i̲I.̲U)AQiJSll&jl#^f T)7

‑i LTISAU)TU)a ^I tbS#i,BJJgmf=. ?3: O _, iE49AtO)i2jtgmf=AQ75) ^{6NP^0)} JFE‑I‑fSP)i)Sh.tgf.,l[f#y;jfJiE11'9‑UJH3AQ(=J.7F;+i)iI)I;a:;iS^a¹^T=tlTf:‑̲illJJ^{$ 4}^1?3. JFti'fF!^I‑.U) AQU)i3}tJr‑‑EI.JI:tLNPt/J(ji:;#.I.:/LTS.[rH4<fLr)r‑Zl'eT/a^I ^{i E=ct} ⁽⁾7F‑y7 ^I ^{7F;> 7} ^{1‑ Sa} ^lT

i^l?a f=&b. AQtiJi;ILibE=iut ^{S a}i?p1^fiE.Ttb^(). 3q:L;i'Tlii2}‑i)iiFi:fLY,j2t.+fxⁱIJ.iiL.l!TE1=

JFE‑l'‑iB)LJLil,i:i);lBf1‑‑^{L TIS} ^(). /I(ii:;;.I.‑‑{T^7=ynL^L TNPt='rTi[':ifjiL.i.5TE^L. ^NP7 =* _{i 9 ‑)I}

}J)L7V1‑:I)qga1/a i.t'j‑i t3a1?a. fI:I)qLT=NP7=j‑i ⁹ ‑)th)LtL iJifil;iTIIU)TIliJl‑‑̲I.Td["lf‑

NPt Ei‑rP;^Eat. ^NP7=j‑ ^{i 9} _‑y7]^)L/)SjkL.''.]L‑fET/u3&Fl!7:rap'!i..i⁽⁾3k1 ^I ^{i E=J=} ⁽⁾^, y[TI‑i

##%itlt*A 6m8. NP##0)CV7?, ^}j:hj ^I‑‑>3 >iEfJif&j%L,f=iZjti&E=

}J L,&1Ei&bS>#iE LfEU)0)tL fEBES m7T=NP7=* > 9 ‑}*)V75S>Kfni=j=? Tilb'9eT 8f=b t3#i,BJJL,f=.^i;2ltO)^I ^tb) ^6, *EEig@to)AQb1 6NP^R75)Ut7,y 7ot=)LBn a)‑JTu+i3dM)i1.Eg‑ET= i‑,5‑iLt14^1. J[Till'.JLI=U)AQ!)iJFE1‑^{* j=tJ{}^I‑ ⁹ ^‑ ^{i L} T[giJ)i. iJif ill&*o)NP^%f##%&= ^SitTU)8 ^I tbShBA675) tf3:? 7T=.

if=, >71 1‑5Ji;j'‑f=NPJ=()S)/i(i.‑(ll;.I)‑‑f']E/)ShFJq7.iⁱfE{Trn^a:f=ti*lLⁱfk(̲}4;xA^fr ^)T,‑‑(1.:S if f=U)gho) ^tf8=BU)Tb, =0)NPO)tfa)J= 5 faZj>fa}j:>J( I‑‑>3 >iEfJitti&

7t!1]Jg a¹fj:7h‑? f=. JR!JLiT.fTr‑r111‑T,nl;n%retti^{f j=T 1} ^I‑ ‑i^a >J.TiiliEJ)LtTin!JitWjlTJJa alf=!)Sh.

A+u[[iJ;=TifIT)‑(7DhA!,a^r=f1:4u)1/Jr.〜dlulf1‑iHi^RL^T ⁱ^lf= f= &b. f a)i;f'‑:a.l[T^fLrH))L17hE=T/u ^I ^{i tit.}

‑c*fx7J'^‑3 f=. I ^U)I t!J, t3. AQU)NPt= kfT/A.1i‑'E':r4‑!J‑:jrJt‑JTJI:i)ih7FTTfp1S^a1. ‑/J(#3:.Ji.[}^r=^J=

()IJ‑)u[T^{i 4}¹^7J.3i;+^{I i=tJ} ^I‑ ⁹ ^‑ ^{i L} TU)i‑:%T'JtEti[;llJ/i:^{a 4}tf=f;3IillriTTtJ)〜)*EfJ[I!^{5 a}ⁱ^/a bO) t#iRTJSmf=.

:iJliLLgf!T)‑AigffTI;JiElai^I.̲7:.a)+^/ >U)JBfi3P)i ^I‑ⁱ pT,)L;i:ulli‑

S / > iEi)t(6^a)/i(a,i‑;;I:.I,‑‑fi3‑IIlt,(6tL ⁿ

‑o)j!J.TiI''J‑(‑i3Jf))^fur:JTLl‑.)q;.ⁱ¹]'f!dil)^t=_ct‑3 T'rTi‑‑J'‑1Ji‑TiE7 7TJI=yF^{L, <} ;;:3il')ifLrJ1.Ci‑TL^)/a ⁱ ‑'5‑i^t331^/a. ^Lf=i)ih? ^T. i;1,.:11IEJ1‑;.I‑A.i‑f.̲5[E=ct‑3 TfU)Jig

‑l'‑1^FiE7.^{i ry)t17h}^t=T/a ^I ⁱ tL JEE+f5di))Ji^ILL;^E=J3^ti‑^/a /i(A,3:;.I,I(‑ia)i:u‑H!7TL‑;ilYi.i'Jli7T/u^{T= &b}

E=iE‑ik‑‑Ttb^/a. ]C*, EE79;⁷ ^I ^/ _{‑)L ti!lri}t7)(ⁱ U)7J(a,::#.Ii‑;3.5‑[IfJ6E=v3ⁱITIIL‑j'‑LEJ‑1'‑I.i‑I‑‑^i7T:

fLYi_j‑‑i^i. /J(i:;a.Ii‑{̲TU),;;uHtfLrfUr.I)kL^L,T=i:‑Jill‑‑[39] _7btb ^(). ;l7l:+1EJ:‑;.I‑I.i‑T‑̲%U)‑LT,:̲llJrJI:i)i,=T;[1H=

i a1I ⁱⁱ^/a. ‑1=.1:I.‑:7?1i.^I.TL;fU)^I ^pT,^)L#‑‑3f‑U)rwrJ[:̲7:rJ.Ti‑i:.+i)ii:iht3.;i‑̲i=7[T7J.i.:)ji:iJu]>'J A(Density ^Functional ^Theory ^:DFT)iA%B] ^i)I, ^# ⁾ >2kV?0)32jtfEBE4hb3hlf3fiE

1?a /)(i:.::3:i‑‑{TS;Lit[4̲(a)'{u+1^‑Ties^E=? ⁱ¹TL‑JF)uLL f=. ).E‑)L'trRla ^E=ti 9tjt1)L ‑}‑ 9 )I.‑‑J̲6‑31G

&r&,qS 8=3ii4qEA& ⁱ diffusionLA& &bDkf=6‑31++G(d,p)2SrAiA& ^&jn) ^, iJLlq&ti B3IJYPfii 7Ti‑JHⁱ)T=.

‑Il‑f2Nk{Trgrll]U)JL‑‑E+fSm)t=ii ;I7L:+I‑i pT,)L*;u‑nt7PT>E]^I‑)‑‑^L ^TL ^l^/a ^I ^{i !JS7.I)}^L14¹^{T i,}^l?a [40]. ^;JTT.:+^I‑^> ‑7,)L3l':u‑Hi‑i tL I ‑7,)Ljf‑7P1{‑I‑J<5}rE.A‑LffU)J1‑;.I‑'Fl'.)E=tit:u3i;:7?_‑Efj:ⁱⁱ I‑'1pi)1jttTt^A ^yJ= ⁱ Flxla‑)L11l', 7H^{j1 i ‑i}^i,^)L^I:.1.t7EEf7=TjTt⁽⁾J4kT ^A ^/u (].:n:7iJ(f!.i1',.i*LYt7:?(J.:(I‑:I 7Jli̲{flTtB^/a. ^{I L} ^I. ,(JliNEznElrWnU)^1‑^> ‑7,)L31;u‑!1t(iI)‑fibs))Lj'‑a)JFE'‑ffSdfJ)E=Fi!J^lj‑

185}1%L5o)IjT‑)V#‑#y.y 7okct? Ti5LhJSm87T=b, ^#) ^> t7k#F,j$13fSj*t=

cE⁽⁾)I‑‑2l)ea 41^/a /)(a,:;;I:.Ii‑fF}S;[IH1<u)5}fL[‑UL3B.;‑f‑?):^fLYi_;‑‑j^I ⁱ ^E=^J= ^(). CVU)#.TT.ILIL+I,t'j.I;5,qL 7=.

2SrAIA&B3IXP/6‑31++G(d,p) ^%jn) 7T=3iij1%ii5i+#iL i+i %f5m81E18 ^{7T=a k}

AQU) [u) ^{() E=}^〜 ^> 1j+ ^/ >(BQ) 7:ym ⁱIT=. 'JjLj'‑.fiJL3B.;‑I.^*:rejr..I:L34 tf=/i+‑/..'iJr‑ii.1J(‑fie.E=J3 i18 &iEIj7‑)Vj!‑ %Fig.3‑4‑1kE4j% L,f=. jlff3:&iE%J#,iR7?#EV1, %o)%3E&j%

L,7T=. Table 3‑4‑28=7k*FE#E%@Ei*Jr3BE8=ct 8#ilES m7T=ySII%‑)V#‑ a ASCFt L, Tj%L, HOMO, LUMOBctV>SOMOO)I*)L#‑j=y ty7o%j%Lf=.

O))

BQ BQ‑NP ^NP

(kJ/mo1)

BQl‑ BQ'p‑NP ^NP

BQ2‑ BQ2‑‑NP BQ‑‑‑NP'‑ ^NPl‑

Fig. 3‑4‑1 Energy levels and illustrations of molecular orbitals ofBQ, ^NP

and their hydrogen‑bonded complexes for the neutral (a),^mono _anion O)),

and dianion systems (c),_calculated ^{by the} B3LYP/6‑31++G(a,p) methodJ

Table 3‑4‑2 Stabilization _energy with the hydrogen‑bonding formation and HOMO‑LUMO or HOMO‑SOMO _energy _gap in kJ/mol unit.

charge

0+

BQ ⁺ ^NP ^0.0 ^363.5

BQ ^.‑ ^NP _‑33.8 ^212.9

charge ‑1 ASCF ^HOMO‑SOMO _gap

BQ‑‑ ⁺ ^NP ^0.0 ^189.4

BQl‑... ^NP ‑130.8 62.2

charge ‑2 ASCF ^HOMO‑LUMO _gap

BQ2‑ ⁺ ^NP ^0.0

BQ2‑.I. ^NP ‑369A

BQ'‑+NP‑‑ _‑414.2

charge ‑2 ASCF ^HOMO‑SOMO _gap

BQ'‑...NP'‑ _‑317.8 ^210.6

a)^Difference ^{of SCF} energies^between the hydrogen‑bonded complex and the isolated molecules (BQ and NP).

Fig.3‑4‑1b) 63}b)8 _cE⁵ ^8=, BQO)%L5I%‑)VS‑iiNPt7k/i%5#E%@Ei*&Jr3BE18

I i 8=ct nfE< ^f3:8. ^a:f=Table 3‑4‑2b) 6, 7k*f#E%@Sj*Jt3BE8=j: ^O *Jr%#fEO) HOMO‑LUMOS y.y 7o&VLiEjli2jt4*Putlqo)HOMO‑SOMOj= ^y.y 7obS>/Jli < ^fa?

TL ^l^/a I t7h L1. /)(,i‑,:‑;i‑‑(TS[If(6U)I.Till‑J2JiffltE7)it[':.')‑^< ^{t3:‑3 TL} ^1?a ^I t7u7.‑,,‑ELiurk4¹^/3. ^g 6 8=32jt4kPhq7?ZB8 85t>IjT‑)Vj=‑j=y ty7oii/JlS < f3:8 ^I i rL 3ZitiE13EbS>df‑}jl

,I7>‑>7 I, LTU)8 I t&J%*L,TU)8. 7k*f#E%@Ei*Jr3BE8=j=8IjT‑)Vj=‑0)#k lE,}LdBttL ASCFTitgm8J= 5 k, qi#%#V>8i2t>#< ^f3:^O, BQtNPO)7k/*#

%@Sj*0)=fEj13Zjt#TtL fERb3TBQ

I ‑

tNP ^I ‑8=3}# ^L,, &3}fb3>P6*Smf=4RPhq bShBb#k7?ZB8. ^L,A)L,, %0)*Fpq#g$8=b7T=8BQ' ‑tNP' ‑kj= OJf3BESm87k a,i:‑#,'T.‑I̲T3L[.fJ1<U)^I I+,^)L#‑ itfs(u)i1, BQ1‑ ⁱ NPU)/I(i!i:‑#.I.‑‑hS['!(6^{a) I} I+,)L#‑itf![i'!‑A:⁽⁾ⁱ⁾ lL::,‑^<. JiB'[':i!)iBQ

‑tNP ^' ‑U)J= ‑jE=)>L.it3'fET/3^E=tL ^I Ij',)L‑i=‑l;I;iiB7:rJ4AtI^(.+4¹^(ilf3:

6f3:U)7 ,y 7ot=)LjiFSyeba. ^=0)7.y 7ot=)L,&FSbSh4:i;7T=LgB)tL BQ2‑tNPO)7k JiRj;#E%@E4*0)HOMO‑LUMOj=y.y ^7obSh/llS^{U) I} ^{t75) 6} ^, ^I,>%‑)V5iLaB%kck 8iE#3}

#bSh&f7T=7T=bt%k6m8. 7ty7ot=)VjiFS&#O&kf== ^tuck ^{O, NPti7=*}

> 9 ‑}*)Vt L,TiK*L,, A? iT=BQ^I ‑ti#L ^< *J[S*tERo)NPt7k,*#E%@Si*%Jr3hE L, =0)iT1 9)V%*%O3gTtj%A ^6m8. J;2ltO)#EBt75)6, NP#if‑FE=j3Ua@e6 iER&to)Ago)&1Ei2jt} ^A ^=X1'i> %Fig.3‑4‑3[=j% L,f=.

One‑clccLron rcduc Lkm rrom clcclrodc

One‑el ectron reduction from electrode

hyd rogen bonding

One‑electron reduction rrom clcctrodL..

hydTOgCn bonding

One‑electron reduction fTrom electrode

..A3‑A."

hydrogen bonding with ncuLral NP

desorTILion or NP anion raica1

charge scparalion

Fig.3‑4‑3 Plausible mechanism of electron transfer from the AQ‑SAN

electrode ^to NP.

I,‑EfW'Ti[MJiAQU)iG7tJ[‑1B[iI;t=j‑ii^{L f= i i,} JiE1'L;)i̲I‑̲U)AQti ‑'[Ti‑fix)‑LgnTAQ ^' ¹⁼

iX7tga ^i?a. ^ff:.l',kL,f=AQ ^I 1iNPt,Jq;.i. l/JJJi:‑a.ri(}S;E't(67Ti‑'[:̲I).k1/3.a:f=tL AQtNP a)/i(a,i:.a.I.‑.I:TS[[;(6)r3l'.U)sis;‑)‑L;a)Jl(I‑^E=i_]‑‑3)a^1?a. ^NP ⁱ /)(a,:;;I:A‑‑;?S‑tf;l1(^{*Jri)'k L} T=AQ ^' ‑U)iBL 7t'[TLi[*:*LY*f< ji‑>tjl

I(7h‑i 7 I‑ L. /JlS ⁱr[‑E1‑!kt‑tL;(̲.lI;TAQ17)i!I=J'Gf41/a.^{'f‑‑̲f'q}^Ea ¹ T=AQ2‑ tNPO)7kii%jS#E%@Si*ti ^h >jT‑)V5iLdB%tlJ=^O fE#bS>3iL* ^L,, AQ

‑tNP ^I ‑0)7j(

/*#E%@Ej*%Jr3BE18. ^{L,A) L,,} 4}7=*>9 ‑}h)VtiiK* L,7T=4kBiiqO)ia5bSh#E7Th zB O , NP' ‑tiiEr&iii575) 6iK*L,TU)<. ^NP' ‑bS>iK#L,7T=iEf@̲to)AQ' ‑tL #L,

< [fJJf1:/iE‑(..'iU)NPt/)(i:.‑3:.ti.f=T5;I.f[1<*Jr9l'k^L ^, ^I ^{U)i} 1 9} )LfLYi&.‑i‑⁽⁾3uT. ^I a)T=ij. 7Ji‑)I jl‑I 7F')7 I,L,7T=AQO)32jt%13E7NP ^I ‑bS>fEBkEmHiJaiT1 9)V75Sh5ffE^L, ^}j:A‑I

I‑ ‑i^a >J;‑Bi)iE7VltliillJJSa¹^/3. ^I ^{U)i} 1} ^}}^{)i tip.y} ^7}t= )LLn,i:+=‑(,TLh7Pt,/i(a,:;3:.lf‑;nEiE=

j=8IjTl)L#‑4XjEt=ck8 ^I,>*)L5iLdB%8=j= ^O ^, jiFSb3hiE17T8 t*k ^6m8.

l1[‑.U)

cE ‑j^E=^, /)(j!,:;;I:.Ji.{}V) /I.'i'lL;utiJ]E‑i71i‑5jijiu)1J.'';jii‑7:r,i&i‑.I;kT/3{=1Tetf3: <. 5ii11nn⁾ⁱ LRt5ih'‑rJqu)JFtEft.:i5ii[,;i‑(Et=^f^< ^3if‑Lj‑^L,TL ^1?a. ‑1=jg.[.5(J!3:.I..‑LlttL^{)il A‑}^{i I} ^=r ¹ ^ty ^{9 tI''Ti} f##tj:A)v,qso) ^1? ⁱ L,TfE4*fEf#&,*0)%#, 3iij1/iRj;ilo)F#q5e8=*JL,T2S*Bg

‑t..n}rifLYi‑)‑‑/I;L/a i)^U) i 't'}‑ALla¹^/a.

;1t5[)A.1:I,‑:&Ii‑.i‑T13

1=l1)FJ)uL7?1iti tI &bE=iJifilf/2[I)a)+ / i i fiTt^k U)/J<i.li:‑(ltiI}‑LI4<)T,‑‑I).:I,‑E=J‑3(+7JrTLij'‑f$4U) }h=X1'i>%FB6b)t=L,f=. ^#) >0)7=*>9‑}h)V, 9)17=*>fEBEk}JFST

?3 =F2r;i‑,?‑Jig‑ffSP)3&frITi^I.i 7J/A,i(lr;^[7J‑(6^a)Il[;.lj‑fJtEa))1iEⁱ^I^E=_ck⁽⁾blUiE7J;=Ti=T‑iSJ;‑)))1&T̲Tl^fr i'i/a^I ^t7T)i[TrJLL7h tfE ^(). f41 L3ti7J(i:.lLlt;()I‑[1<U),Jq;.i^(=cE‑3 I)(i ^< :),?(I/fjil3:1'igat

?a I i/)i)Ji7h‑3^f=. ^{9 1} ^7' ^II.i7J(i:;Ill;I‑5‑f]hE!)ihi3tlL17)Lj_‑)Lfii tl7)i.i.A‑j^L. iGi‑}‑LJ.7rlfll.I;

CiT:̲N.1Jf=iSdi'))I?a^S)^{a) a)} r]Jl[rie^E=^[R‑̲)llJ^{a 4}¹^yi)=f2r'!‑,?‑‑JrTLi1'‑i$4U)3&FE A/f[.)I:yJii.znEi7:I^A ^/a.

9 1 7l‑II ti⁷ ^I / ‑)L7k tlu)lt.fi,1n'.J/i(,i:.‑(ll;.l7‑‑T')LE7Ji.‑jj;.i17J(a,:;I)I;(7‑‑[4<7V)[i‑.A‑j^L ⁺ ^{/ i} 3E;

}‑LIBi/)(A,:..[lf;I‑j‑(4<!)i.]qiLlfH 77̲f1‑:)H^7=r)Jt^L. =fi¹ J3iLR",)ITS2 iEi)‑L'[Tif1'/:/)i]5f&^L. ‑fxrLBi?

=JiE+fSP)3&7rI1:7:rf'J':7Jii./LTTb/a.^a:T=. 9 1 7llIItL I.TifiSP).;&FI‑7:E=7l‑D^I‑>f$4U) 7VTnl‑I)‑‑17Ji,i‑nT.. lit,1ilJT‑nllU)_cE^j fj:.JS.ⁱ^l/J'J:;(ill:I)‑‑(4=iJSJf:‑‑().:17J.Ei‑{} (=thdli!1JJ^{$ 4}^1?a ^‑ FiirL[:i‑,?=J.‑E+4Sdl))LL‑I,i:T.35/a.⁺ ^/ >7T)iJFE‑f+ f I)^7‑ i L TfiWtE ^LIL l7JL{LLT:7?1L + / i ti ‑I.Td‑ii2J‑t[6i:,LJFE1‑'‑iX}tl1<Tb7J[Ti[r1'(‑5iiL.;.5‑fE:TJ(‑fig.7=yi#TjiEFf^L,^I ⁱ^1?a. 1<fUF‑

J)uL#.ri^Hl‑tL ‑)J;‑‑().:5ji+ⁱ a)A(j!i:‑#,I...(̲}^ti^I ⁴¹t3a)I;‑tip(r1'(.5iit}.3‑fE:1M!ELL.(=lPf^{L <} ,r;16?I,Ji^L. ^f4 ¹^fla¹

LIB‑jj:7Jr:a‑T‑i3@‑))^{X ]7}^I ^7lttL1^7Ti‑^l7‑‑A^/u ^I ⁱ ^7Ti‑_,T{^L ^I ^L^1?3. ^{I L,}^I. ^I U)#,f...ill‑tin‑‑̲JTI!7lT;‑Jfli S / i ^a)i;qiT'JtE7:r5iillf;33l.Lrif J)7J(*i:‑;I:.ri.J'F}7Vlf;‑lJ'T6P^L. /:Eq:nlli{i'1!J;>Tl‑Tf.:[iJ5U)ffQ:fJtE^f1‑[J‑^l}‑‑^L

TU)8=ti=}JFSL,TU)8t%k6m8.

:I)‑.JFE1'F!^I‑̲^T=^* ^{/ >} 7:rA+uTfi^L f=AQ ^I'l‑Ll3:fLil.'iHEiii'Jji‑I‑J).;lifi2{fT!TliJ,Tilt‑!'gky⁾I)i^lf=7J(a,:;;I:.Ii‑(i

a)()FJ)uL7?I.i /J'J.::#,I.‑.{T^I ‑T,^)L‑i=

‑ (I

cE^/u 5}‑i.il,a;:t!it^l=I.Sjtⁱ ,;I;u^5lbt't‑n'Jt=I.TL;+fSqU)7:rn(T'JtEⁱ TZj.Th'‑iSJU)A +rLiJ(I.!irL1?a^I ⁱ ^!)iTt^ff=. IL>U)3:,Ji.‑H!.i‑l7hti‑[‑̲7ty 7't )L i‑[r''J^U)J,‑‑a

‑ffSJ;‑))JiI,i:7TJi,;']u^,l',t';R'.)E=:tiFf=r^L. /I(jlJ,;:a,li.(T7VIJ[TL;ffSAU),rJF^‑rTIf^U)i̲Ji'f':rlluT‑HJrJ[:̲^a)^Tr'T1^[

‑̲ i ⁱ¹‑j u

n'JU)3>fl tift. _ck⁽⁾i.L'i1'[VT(Fl'JE=JFEjli$4i))frf[[1nt^L liG'fi4‑!J‑:btt̲J[JI:̲fly/I‑‑..#[.[^rlL TL ¹^/a I i 7hh53i 7h? T=. rJJ‑̲f'.)T:t3a¹f=*.I.:^LIL‑I.i+ ^{/ i} U)I;‑E:i‑([EJti.I,U)*t3:tlVli[4=F''!JiLF.tt;+fSJi)),%a)PJ:[!‑

lJ7.E=‑);!;h!1n'J5:nl‑i7:rI‑J‑‑,‑I,i.ff=P],'f‑fJ7.a)f=&5U)tj=h)[i1'7;i L I̲iTEA‑.7:tb?a i ‑'t'j.RLL14^1?a.

'J;I.Fn

1.=*0)S&

a.iie#

1. anthraquinone (M.W.=208.2)

+I) 9 1 jl7, 9 (i:1i)_{7h tl}rI]‑!1)i$4^1TL l/3j'iti‑Liii.7:r&[HTfI1/̲Ill‑i.LT= S̲)a)7Ti‑tf)ll^Lf=.

2. methanol (M.W.=32.04)

j‑A 91 5=X9(i#)b1 67fBRSmTU)8XJi9 T,)VJBiR*&%0)5:3:B!JB ^L,7T=.

3. p‑methoxyphenol P.W.=124. 14)

#RIEBEIX (Mi) b1 6ifBRSmTU)8iR#%JE‑0)a:3:Bfjq ^L,f=.

4. Phenol P.W.=94.ll)

)i‑‑)]'.,'fEr)k13iti:(i:1:)_{7h t1}‑Hj‑tut^{5 a}^lT ⁱ⁾^/a i‑Ji;.iLifLYX([Hhli#.I.‑‑[["T[^L TIJi[r7^{L f=.}

5. benzoicacid P.W.=119.12)

j‑A 91 j=X9 (8R) ^b1 6ifBRSmTU)8aie#&7j(T&B]i5#E[]Fj[]L,7T=bO)&Bfjg ^L,

6. 2,4,6‑trichloropheno1 (M.W.=197.‑45)

j‑*91jlX9 (a) A)6ifrRSmTU)8iR#i:%0)3:3:BfjRL7T=.

7. p‑cyanopheno1 (M.W.=119.12)

j‑i)91fX9 (iR) A)6ifBRSmTU)8iie#&}9/‑)V ^:7k‑ ¹ ^: 4T&B]i5

#E[]E][]L/f= b 0)%B!JB ^L,f=.

8. 1,1,1,3,3,3‑hexafluoro‑2‑propanol P.W.=168.04)

#‑>9)7k3f (a) ₇₅₁6iffRSmTU)8iie#%%0)3:a:BfFq ^L,f=.

9. p‑nitrophenol P.W.=139.ll)

+h5J{j:R9 (8E) b16fF,BRghTLt8H*%$9/‑)L ^:7k‑ ^l ^: 4‑T'&E]i5 kE[]E3E]L,T= b 0 %1ff7] L,,T=.

10.p‑nitrobenzoic asid P.W.=167. 12)

j‑A 91jlX9 (i#)^b16fFBRSmTU)8iie#%T&Fi5#uEj[]Lf=bO)%jfjg ^L,7=.

b. i}1 9 T).y9ji)V9t9h'i>(CV)ifUJk

1. Jr‑Elijli

4fjgiEi@ti BAS(8#)75) 6fFfRSnTU) ⁸ 9h'9.y ‑>‑A‑ji >iEi&(q)1mm)%7)VS

+7?+5iiE=fUr.li'̲..:^L I(4fFIJ^{L f=.} 2i;J!L:i/;tit‑L'9i(iFc/Fc'J.TJll['di'=y)fH IT=. Nr4jru4'[1)7tir11>:#!i!

%B!JB ^L7T=.

2. 7‑Ef,=f,T))VO)R9g

j‑*91jlX9 (i#) A)6fFBRSmTU)8XJi9 T,)VjB#Jr%iie#ktV#19‑‑>

‑ 713A) ^{7:r^a} ^1. [I.T'‑VtnM(^*Lri‑J‑‑i^l, ^I U)iJ,Zfil/2,+I;,'!TH=!J'^E=_ct ⁽⁾1l:Jfil‑.'b!T/u.

3. Tetra propyl ammonium perchlorate(TPAP) (M.W.=285.7) (jEFqiE#Ef) 0)%hk

ドキュメント内生理活性キノンの水素結合やプロトン移動と共役した電子移動反応に関する研究 (ページ 31-86)

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