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

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Title

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( 本文(Fulltext) )}

Author(s)

勝見, 次郎

Report No.(Doctoral

Degree)

博士(薬科学) 連創博乙第2号

Issue Date

2012-03-25

Type

博士論文

Version

publisher

URL

http://hdl.handle.net/20.500.12099/42970

※この資料の著作権は、各資料の著者・学協会・出版社等に帰属します。

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-)L&ll::;ti'Tl'i)ji:rEti'Tu)[TL/T=rTIfE=tiAQ a) -i[iua)t'r%fEiEi)til.kS)

2;fji-}jlJI 7h>->7 I, L, _{I?0)&1biZjti&tiq39.EE%6hTU)f=.} 91 7oI _7?tL

(7)

@Jr%LiO),qgU)7I ) _{-)V*75Sh32<kj}L,, Fig.2-1-2,3 _7?j%1j= 5 k, _{iB%E5iBbD8=J#U) AQ}

a)=il:i-LJ7Ph7tD- TitE=fly3 _{I-il_iu E=r[''l7))-3Ti3@-))}LTL _)i, _-iFjLu

i:=ilRLV);7--} L,TU)? f=. SiBLi#E7?ti-i&B t5=j>i=7--} L,I, fEf}51&bS1%fgL,T=-?0)q

i9faB2JE3Ziti& a,ji L,, Jf-0)iEf)iiL@b16 -[RPFEib=%fjiFSb3>G3%7T= I i b3>#5u g m7T=.

9 1 7JII -e.tL

Ir.TrT[JT,∼;Ll;-E=JJq;.iIJFti+r&,i[iJf--_fr1-7..?F;.rJJi)igu)-.}q;.i17 I / -)L ti.:f1:J(JP51;Pihk4:JA!

a.S&f3: 2fo)A)Vji _{>&3:B,bS>i2kkj}L, 7T=.91 _7oIII0) CV *&0)g$1#ti Fig.2-1-4 _ilLj%1 cEj (I. /I(ji:.-fll;lj-I4<U)tI,T3)3gU)i.[.l','))[1E=[1':?I AQ a) =i11u !Jit;Fi-rtL [iJ]lJ:.iE=-iF:Eu cE()

b#-}jlj 7>@.rJ8=#7T=f3:&1E32jti&b5TtHfRL,f=. i 6 kie&b3hS< fEa i, AQ

0)-ilkEI_{a)t52(EiFk/JilllJi-)i}L CV _{U)JL-Bit,iE[&!JHI}Jll':-_iluT/ai AQ (i=JFB'-fig-jag41f= U)_E=JJtf

L,, i+FS18&1EjiFSbShfbbT7b- TihT,fEf}iiI@b/JlSU). _?a: O 91 _7oIH7:,[L

AQ ti-1;_{I.IjCr]'.JfiEB2[Eig)i-)L{)JL;,i->Ji}Lf=. I _{U)l!,lJ.-r7;]tiiH}-Lgatf=}AQ ^7-'D I->iJiiS

Ji))L , TIiB,.2[E)1&fL!E=J3L IT7-JD 1-i,2JiF[1</)itJjE-:]'L-_r]'Jr=().---(IiLfj:i lf=&5. 7-lD I-i)]L;aL.''ifE

lil,i:7PiI_r.tdiE=fI?f= i-'EjiL L141/a.

I a)cE :)E= _AQ V) CV _{U)-'i.-;-J3-)Jib})r1--().--I/a_{/)(il,:.-(ll;.-I-j-[1<V)F2JJJr-._ligu)i)qti}a E=cE () 3 9 1

7o8=3}*18=tbS7T1%8. 917o I Teti Fig.2-1-1 _7?j%1j=5 k}9)-)VbS3f#

18j;B%T,. 2 i&BO) CV i&bShj{-}fJI 7h->7 I,T8. 9-f7oI7?ti Fig.2-1-2 i

Fig.2-1-3 _kitlct 5 8= 2?0) CV i&bShy-}L,T, q3ya&1Ei2jti&bSh%iRUSn8.

9-1 _7oH7?tL Fig.2-1-4-Fig.2-1-8 8=j%1j= 5 k 2 i&0) CV _bS7--}T8bSh, _%oB2

Lb32jti&tii<q397:.b8. =m6 0)91 7oii Table 2-1-10 _Tj%T _pK 8=j= O EiBuT8

I _{i 7u7tf.} )f1--i).:T7JEfTrF)a)/J(j!.:;[lI,:ij-iJJ:_f']EU)iJqt!S (=J= (), CV 7htitECf= :,i(;JU)'=r

'T(L

f=. =m 6 tL AQ Bj=V?0)i2jtj*0)7k,*#%@Ej*fEBE,*i:%tp&LE32jtjiFS} A

=Xi>b3) 3 91 _7o#iE18 I i i.%* L,, _{7j(iRj;#E%0)#LibS>AQ} _O&1biZjt} *=Xt'

i>%STJ1#LTU)8 t%A6m8.

a:f=, _{=UyJJiti!t'itiryjWEE=[X;L))?3}I t!)iTt5ilt. I41f71U) 9 1 _{7l=lu)rITf7n7Ti-t7Jii-n}

b#if18. 5(]ktj:A,Fig.2-1-4, 5, 6, _{7Tej%1j=5fE*B%Tlb8bS>,} =m6ii91

7ol t917oIEO)*Fpq7r,ZB8t%k6m8. _{->7)7I)-)V%3f#S-&f=t%,}

-i!kU a)iVJ-E=iG)-til1!JiI/J1S< Jl-l41TLl/a I _{i/Jl t1 9 1} _{7dE=)jii!(iT/a} I i S)rEt-i/JJi.

Tt::;i)T3-)ji:(-(--((-:I,-T.U)CV _{E=J3t+/uBiiIEil1/Ji71D-} tit.tiEL)_I _t7h _{L1 9 1} ₇ _I _{a)rllHS]497:I}

b8 _t#rlWL,f=. _{)RkJt#i}7)V*tj7oT]/i)-)V&##Sif7T=tf,} aiBEFLXT7?ti

A,f2fEia/)S7b- T{t=fiE-3 f=/Ji, (ltf'T3)ig;.Jl/'UIR3:Tli91 7'lI V) _{1,TSdT))furl-1-}LIL 1/3 _I _t7)1

6, _=mb917ol tIEO)*FBq4gTlb8t#uWL7T=. 5:7T=, NP

_&##iiff=t5ti

91 _{7oHt=iEU)*gb%j%L,7T=.} =m6 _0)*Fp]4!R &91 7oO)&1E32jt}b=xt'i>0)

i.JT-1f'-:Eta/a_{i ,L'}-ALla1?3} I _{t!J, L3, InftalU)} fh=7ltilE=f_'I!U L. _{)'4'f.I-rT7=rf-iT.-y)}I i

bShiEf7f,b8 t%k 6m8. ia1&8= Fig.2-1-9 8=p-I h _{tj#,e,*&%##git7T=} t%

7:t357JJit, tlu) 9.1 7ll=i)I.([.:a fl ilqL!)-:yMj:CV 3i.rid--))7:riJ-ILf=!)it, I a1_{tiBjck1:I:_liHJSIf}q;.I}

(8)

-i L TU)1!)-:Jrl:_*L.I,J-1-1t=ti _{/J(i:,i#,IT:{}}*Jl[;.-Lj-T/3 _{)-JLiU)ll:_fV)ST._[-AtTt}_A /u _I _i

7P1,i:Jq2?

galf=.

(9)

i I.. . 1 - Om moVL - 0.Dam rrLOVL - D.lDrnmoVL - 0.2L)mmouL -- O,3OmmoL/L - o.SOnlmOVL - 1.OmmoVL. -1.5mmoVIJ - 2.DmnlDln. - 3rOmmDln. - 4_OmmoLL -7.OmmolJ1. - 15mmol/L - 20mmoUL - 30mmoyL -.4OmmouL 6Dmmon - 8OmmoVL .let)L) -1400 .l600 -1800 -2000 E/mV vs, Fcqc+

Fig.2-1-1 Cyclic _{voltammograms} _{of 0.2 mmo1/IJ} _{anthraquinone} _(AQ) in

acetonitri1e O4eCN) in the presence of various concentrations of MeOH.

Scan rate :0.2 V/s. Electrode :_glassy _carbon _electrode _(GC) (q)=3 _mm).

Supporting _electrolyte : 0.1 _mo1/L _tetrapropyl _ammonium _perchlorate

(TPAP). 25 20 15 10 < a 5 tLtt -OmmoLIL - o.D5mmo1/L - 0.10mmo1/L - O. l5mmol/I, - o_20nrrLOl/L - 0.26rnrrLOyL_O._35mmoVL - U. 50rrlmO1/L - 0. 75rrm10l/L - 1.OmrrLOUL - 4_Ommo1/L -I.5mrnot/L - 5rOmTnOlnJ - 2.OmmoLIL - 7,DmmDl/L - 3,Onmol/L - 9.5mmolJ1.

_800 _-10OO .12DO _-14DO _-1600 _-1 BOO -20OO -22OO

E/ _mV vs, Fc/Fc'

Fig.2-1-2 Cyclic _{voltammograms} _of 0.2 _mmo1/L _AQ in MeCN in the

presence of various concentrations of p-methoxyphenol.

Scan _rate :0.2 V/s. Electrode :GC (q)-3 mm). Supporting _electrolyte

-,

(10)

2.5 2l) l5 u1 i a ,. tt - _ummo)lL - O.O5mmoLIL - O.1ummoVL - o.15mmot/L_O.20mmoL/L U.3OmmoUL o.410mmDLIL - L).GOmmol/L - o.z3L)mmoL/L. - 2.OOmmDUL - 1.OOmmol/L - 2.50mmoUL - 1.2.5mrnouL. - 3.OOmmoVL - 1.aOmmot/L - 4.OOmmDUL - 1.75mmoLIL - 5.OOmmoVL

-i.10L) -l60r) .18OO ,20uO

E/ mV vs. Fc/Fc+

Fig.2-1-3 Cyclic _{voltammograms} _ofO.2 _mmo1/LAG in MeCN in the

presence of various concentrations of pheno1.

Scan rate :0.2 V/s. Electrode :GC _{(q)-3 mm).} Supporting _electrolyte :

0.1 M TPAP. < a ht 25 20 15 10 5 0 -5 -1O -15 -OmmoVL - 0_D5mlnO1/L - 0.10mmo1/L - O,15mmollIJ - D.25nrrLOl/L - 0.35mmot/L U. 50mmotn - 0.75mmDyL - 1.OOmmoL(L - I.5FrLmOVL - 10mmoUL - 2rDmmol/I. - 15mmot/I. - 3.DmmDuL - 2OmmoJ/L. - 5.Ommol/L - BOmmoVL - 1.5mmotJI. 5OmmoLll. .loco

-12OO -14OO -1600 -1800 -20DO

E/ _mV vs. Fc/Fc+

Fig.2-1-4 Cyclic _{voltammograms} _{of 0,2} _mmo1/L AQ in MeCN in the

presence of various concentrations of 1, 1, 1,3,3,3-hexafluoro isopropano1.

Scan _rate :0.2 V/s. Electrode -.

GC _{(q)-3 mm).} Supporting _electrolyte :

(11)

25 2O i a i 15 ILL -Um not/i. - (H)5 ml7n1/L - L).lDnmoL/I. - ().lf)mmoU1, - ().20mTnOIJL. - O.30mmot/L 0.JLOm molIL - 0.5OmmoUL - O.7.5mmoVL - LOOmmDVl,. - _i.50rhmOLIL - 2.OD rnTnOIA - 3.ODmmoln. - _{4,OOmnotn_}

_1OOO -l2OO -1.1()O ,16OO -lBOD -200O

E/ _mV vE,. Fc/Fc!

Fig.2-i-5 Cyclic _{voltammograms} _of 0.2 _mmolJL AQ in MeCN in the

presence of various concentrations of p-cyanopheno1.

Scan rate :0.2 V/s. lnectrode :GC _{(q)-3 mm).} _{solvent-supporting}

electrolyte :0.1M TPAP. Z5 20 1.5 <q u) ht 5 D -a _1O TBOO -1 DOG -1200 -1400 .1GOO -180O -2000 -2200 a/ _mV vs. Fc/Fc+

Fig.2-1-6 Cyclic _{voltammograms} _{of 0.2} _mmo1/L AQ in MeCN in the

presence of various concentrations of p-nitropheno1.

Scan rate :0.2 V/s. Electrode :GC _{(q)-3 mm).} Supporting _electrolyte :

(12)

25 2O lr) < 1tl a tth ∼ :. - (]mmoLI[, - U.lrrLmOLfL - ().zmnlnLIL - O.:1nlmDVL - 0..1rr)mat/L - 0.I)mmoLIL L).(TrnTT10UL. -u.7nlrru)L/L - H _{PlnlIllL-LIT.} -L1 ,!IrTtmrILIL -I,OmrrLOLIL - 2.ammo)/L - I.2mrrLDt/L. -.1.Ommo1/L - I.4rnmotJL 3.5mmoLIL. - I.6mmot/L ----A.Dmmot/I,. - I.8nlmOUL 5.OmmntJL. - _L2._OmmoV]. _{6. Onmolll.}

-6()O -tiOL) _-I DL)O _-1 2UO _-I ,I(1u _-1 GOO _-1 tjUO -2IIr)U

E/ _mV vs. Fc/Fc'

Fig.2-1-7 Cyclic _{voltammograms} _of 0.2 _mmo1/L AQ in MeCN in the

presence of various concentrations of 2,4,6-trichloropheno1.

Scan _rate :0,2 V/s. Electrode :GC _{(q)-3 mm).} Supportingelectrolyte :

0.1 M TPAP, 1D i 15 tttt D -LllTHTIL't L - O.O5mmolJL - 0.1OmmoUL - _{0_15mmolJL} - 0,20rnmotJL - 0.25rnmon_O.aOmmDLIL - D.35mmoLrL - OAOmTnDl/L - 0.45mmDIJL - Oy50mrnolJL _GOO -BOO -10OO -1 2DL) -1400

-16DO 1800 .2OuO -22OO

a/ _mV vs. Fc/Fc'

Fig.2-i-8 Cyclic _{voltammograms} _{of 0.2} _mmo1/L _AQ in MeCN in the

presence of various concentrat,ions of benzoic acid.

Scan rate :0.2 V/s, Electrode :GC _{(q)-3 mm).} Supporting _electrolyte :

0.1 M TPAP.

(13)

-6UO -8DD -10OO -12OO -140O -1GOO -l8DO -2DOO

E/ _mV vs, Fc/Fc+

Fig.2-1-9 Cyclic _{voltammogTamS} _{Of 0,2} _mmol/L AQ in MeCN in the

presence of various concentrations of p-nitro benzoic acid.

Scan rate :_{0,2 V/s.} _Electrode :GC _(q)-3 _mm). Supporting _electrolyte :

0.1M TPAP.

Talble 2-1-10 _pK Values _{of hydrogen} donors _estimated by _calculation

program, Advanced Chemistry I)evelopment (ACD/Labs) Software

Vll.02 _{(1994-2010 ACD/Labs).} compound pKa a methanol p -methoxvT)hencII pheno1 1,1,1,3,3,3-Hexafluoro-2-propanol p -cvanoT)henol p -nitroT)heno1 2,4,6-trichlorophenol benzoic _acid p -nitrobenzoic acid

a)Refereced from SciFinder.

15.17 j= 0.10 10.40 j= 0.13 9.86 j= 0.13 9.75 i 0.20 7.79 j= 0.13 7.23 j= 0.13 6.59 i 0.23 4.20 j= 0.10 3.42 j= 0.10 Fig.2-1-1 Fig.2-1-2 Fig.2-1-3 Fig.2-1-4 Fig.2-1-5 Fig.2-1-6 Fig.2-1-7 Fig.2-1-8 Fig.2-I-9

(14)

:LJli__{LL^n ij5lL,}_{l/I(j!,i[lll:i)-.l1=-(i.:(LIT}r=J3 L1?3 L l{ty 9 71 i I)I _{7ltlLJ)PJ.'r'.frr}

CV fhr= J=yJ.Ti3<t[EJti{,itll]JJjE8LJ[TL;+iSqU))iFL<U)[nJV-FIT.t=[,.i(alT=1y-)LT.A yJJi1. rHHc

a)lil,i-JtTi!)S7i,:(I!T/Jii-I_T.CV _U)i1:kJFWJ,_Ll_fU))i-a: * _{∼ =7:Lh} _7:r4=!ii1/aI i tar-)!fE.L

U). %0)FIB, =0->=1V-->3 _>%175 _{=t7?*%0)jiFS}*=xL'i>%#tW18}

I i *LY6-it.#f=.FR(I _{-> I} i L

--> a > _7:yFl)i_IT't+ftTtS/ _{i:.-i,ti-:.i?-(1=U)}_{=J[lifl3J;-)JE=J3t+}

yJ[TiL5(-(fEJt}',n'J4L-!]-:JrJl--_fLYfUFJjkLL,f=iqi;I;-[27] /)i)A(), 7'-lu I->FSJi)))jl,i:i;J1(BJIkJi),i;u)LT.:.

-&7-JTJ-lil)i11'B1-r1:(-JLSa1[28]. -> i i L--> 3 _{>V)IJ-JHiJ_l!7JiI;iB<tlalTL}1?a.

-fJ2l=iJi;iYklIIa)B<i[Ei3J--tJx-hL-1*LY,i-{TCV a)J,-BtiE

-JFE(1JI-.[1fTi'r;!ti.r,-.i-CE= ,i-,-TJ;-iit*t(Lqt' (A cm-1)0)jETiET I tbS7,i 8. i-

(6.02x105)

n3/2D.1/2vl/2c.'x,ev

I I _7:.7Jiln ti'r-E1'[T)uL*-_),i;t=

-13i,i-yJi-TJt:Jig-fR Du tiJTLhtJLJii:2*(cmj/s),1,t.ir-i(iI;i.l7.L'lIiA3

EFLRN/s), C.'_{ti@1bi*0)i*%*i@tlBE5} _(mo1/cm3), X,ev ti Nicholson-Shain _0)%fJitLq

&[J=x(a)reiiSm8FSFpqO)1q&7?ba.

3:7T=, &1Ei* ti2jt4*0)%r@iiajBEE

(co,cR)

tiER&fElkE mtiTEEO)i,-)V>X h _0)iETiSm8.

fa

-exiZ(E

-Eo))

CR

*)V>X hie*0) n ti##iEf&, Fti7 7 9j:h-E&(96485 C/mo1), RtiTR1Sf&,

Ttif[t"'LliHK).E' _{tiyWEiB7tJ[TL;I.tI:(VrEt}A?a. f''t--3 I , I-T:;'LT.-U)I.TLi1-r',)iJ[;Ef.rI:(;J3ti-/J[Tii1'iE(Ll_'J-_t'

ii. )i(1JL;(EJ:i-.1.TJ.WtllTnA-J3i: LR'BllILiBJ-LJr-';ifL LIL;_{[liJIJii;1,,)A.}I.,i;[1JI-A:Hi,3I.tdiriEU)/_{i j f}

-9

-fLY-i.i i L--> 3 i (=cE ()i)tJJjIT/aI tTt_A,Ff7[[[1r)T?aI t7Phref/3. a:T=. B-,2[EiG!7t)i

I,i:iR (I/J'J::;'Ji-/nL5;[tfI6!I=J)eiR.7: D 7-> _{fSP)Ji 1,i:}A *LY_{(_7T;L1'--f9-i)Li}_ILL(_a *Lr)t'}.

1.[i;:L,I. _/I(j!.:;

[lI;lj--l1(().--(lfI,-E=J3(i-/aCV a) _>i.($4f))fLY_rliJFuT/aI tTt. _-iij[u)ILJ;i,I-I)ilJL:I JJI 7:Ll *JT(:-_ iP,TJT8I tbShT58.

4>B], AQ 0)g21E3ZjtEiFS,% k7j(*f#E%@Ej*fEBEEiFS,qSBckV7oT] I,_>##jiFS,%

7=rg:[L*fi3-)ifT.AQ U)I.TJ-ffSJU)i I)I _{7,1ILJ)PJ,'F.tLJT-}_7i.Tlf:]'.-3 f=. AQ J3 J=LRtAQ iBULJ1(!)i

)E-Zl)q1/u

7l(ji:.#.f.-.{T5['f[4<U)F(;IEiE!J-t;i JJI _{7:LJitl[J-Lt.qJ-Tt;d3<f=}a: -jE= 3 9 1 7'lE=5:)i13.!fiT

8 I tb57>f, _{%mfnO)qS#fa@4Ei2jt}*=Xi>8=G!E)LTU)8} t#f,qrJSm8f=

a, =0) 3 917oe) CV 8=?U)T DigSim _{7oT]9h'9i>7:,->SIV-->3} _>%11U), iE

-Jlf3JiJ)f i)I 7:LJ)P1.'II-I-rr*/(J--? T=. _{/J(i:-;I:.Ii-(}S-[If(6*Jr$l)k}L T=# / > U)r11F1[Ei2)tiGJi7F

-}51JI 7h->7 h L,, %0)@1Ei2jtfElkO)##tL T%eOie7?ii1= tbS>7?%8 [19].

^r

_

RT._1+K[HD]n

AEl/2 =

-flnF

_"1+K-[HD]n

(15)

DigSim _->S i V-->3 >8=ck m7rq:6n8 AE&Vh KtL =0)rR%ie&ct < iifRL,T

bl O , CV i DigSim ->S i V-->3 >1a I ttiBi5FWfa&1EiZjt}h=x1'i>%#FA

T8

_E7?iE,f7;q9(fE'y-)VTb

8.

ti L; &bE= 7 )i j _-)L _1,t!llJliftU)/J(*i-;(lJ;.I-}--J(Jl:_a)4-!gii5_Till.iil_{(E{?rW)ST)Jili:1'i}_{g a}i?a 9 1 7o

I_{t=?LITA,'f'llJT.,=rf-lT--3f=.}91 7' Ia) CV _{a)T!)-:ill(i.}AQ rTJfit(kt=f 9 _{/ -)i} _,=ri,Tu)I7T

8 8=aU), AQ 0)9x1 7=*>fEBRt=j=8=i&B 0)q39fa&4Ei2jti&bShdf-}jlJI 7P')

7 I, L, i 68=i&#uO)}9)-)V&bDk8=tTI, AQ 0)7=*>9-}*)VfEBR8=}+

I,i:L 7=--.ilku a)

rlljgflB'2IEiE;-}-L:illS_)(rrI._T;?T),E=7f-}j1,(7L-> 7 I,1/3 I tret35?a. I U) rll

3gr%bS>6U=mf=917o I 0) CV k?U)T->= _1V-->3 _{>%1?5kzB7T=O,} #/ _>3Z

jti6t} 9 / _-)VbS>Bij(T 1 : 6 _{0)7j(*f#E%@E4*} (J22lf1 : _{X@Si60)Sie8=m81)} &Jr3

r)kT/a [20] I t7Dt,)-{g4tTL )/a I t7htL. r[-']1-:fu=lli^7:.i :6 5Lrf[4<*Jr-2l)kTZ/(--_I),k

,*%*@.L,f=. AQ t}9)-)VFpqO)7k/*#E%ii49AbT,q9< , ->< i V-->5 >0)#E

BL AQti1 : _2@$4*, AQ7=*>9-}h)Vti1 : _6@Sj6, AQ9)17=*>ti1 :6

@$4*%Jf3BET8 Scheme 2-2-1 t=/jtT@Sj*fEBE,%bS7%6m7T=. 3:f=, %0)tfO)&4E

iH)tJ.;Ef;I-_J3J=Utf;I.fl1</I--_l5qk'&fLYTable 2-2-2 l=,litLf=. =a i_{LI U)fLfiE=i:}()_fI-LVJlai/u

->

i i V-->3 > CV dh#R Fig.2-2-3 8='j%1ck5 L=9S&ul&tj=U)-&&/j{L'7T=. %0)

f=i5. _{-> i} i L

--i 3 i _ret7t.)I:_LL31T=PilF1[EiH)tJiEI1'I-_i-3J=VtS[';l4=/:lil).kJl;EE(7btE;I-3jfit(Bret35

/u _I _{t7hL,1t$41f=.}

-> i 1 L.

--i.3 _>Ttf'J':_tla1f=#illl-7h_L1_:)(U)I t7PL,I;-J,Q:i$ 4 1f=. _{/)(iri-;;I:.I.--}:-}if-(Jff1<*Jr$l)k

L,TU)8}9)-)V& n b57Bk8i=a:?I, AQ _{0)&LE3Zjt%1ktij{-}jlJI} 7P;)7 h

18bSh, =nti AEO)iebS>>j(a)j= 5 8=iigm,

AE 1/2,2 RT._ln 1

+K1-[MeOH]+K.-K2-[MeOH]2

+...

+Kl-K2-K,-K.-K5-K6-[MeOH]6

-F

lil

1.

_Kl2-[MeOH]'

K.2-K22-

[MeOH]2...

_{K12-K22-K,2-K.2-K52-K621MeOH]6}

3:f=, Kn _{'Kn-'Kn2-&V'Kln} _{>K;7>K,n>K.n>K5n>K6nTIb8=tb'6,} CVO)->

7 T- tcE < _-fiT8. }9)-)V[iAQ t7k#Rji#=%@EjS&Jr3fiET8 =t8=j= O, _AQ

a)@1E32jti15E%ji-}jl-I 7P;)7 h Sit, 4Sk AQ 7=*>9 _{-}h)VO)BiJE3ZjtfE}

I5E%j(i < _->7 I, SifT=f=b AQ 9x1 7=*>fEBE%itT=i&BO) CV _%j(i < ji-}

(16)

A

i:ll

7l-K"1?

LPE)2 E10 Ell E12

ATT:;

1 A

Qtt-;T2

E AQ'--PE)2

TtK2

3 AQ'--PE)3

TIK2

4 AQl--o4E)4

TtK2

5 AQ---PE)5

TIK2

6 AQ'--PE)6 E20 E21 E22 E23 E24 E25 E26

AQ2-TIK3

1 AQ2--ME

TIK32

AQ2--pE)2

TIK3

3 AQ2--pE)3

TIK3

4 AQ2--pE)4

TtK3

5 AQ2--pE)5

Ttk3

6 AQ2--pE)6

Scheme 2-2-1 Equilibria involving two-step _one-electron transfer _and

formation _{of the hydrogen-bonded} _complexes _with _methanol _PE).

(17)

Table 2-2-2 Estimated hydrogen-bonded _complex formation _constant

and electrochemical parameters giving the best fit simulated

voltammograms illustrated in Fig.2-2-3.

Calculated Parameters _{of Redox} Reaction EO a c[ ks E10 _-1.32 Ell _-1.27 E12 _-1.21 E20 _-1.87 E21 -1.78 E22 _-1.69 E23 _-1.60 E24 -1.47 E25 -1.35 E26 -1.26 0.5 0.15 0.5 0.15 0.5 0.15 0.5 0.05 0.5 0.1 0.5 0.1 0.5 0.1 0.5 0.1 0.5 0.1 0.5 0.1

Calculated Parameters _{of Equilibrium} Reaction Keg a H kb Kll 0.35 1.Ox107 K12 0.3 1.Ox107 K21 3 1.Ox107 K22 2.5 1.Ox107 K23 0.8 1.Ox107 K24 0.1 1.Ox107 K25 0.05 1.Ox107 K26 0.08 1.Ox107 K31 95 1.Ox107 K32 90 1.Ox107 K33 25 1.Ox107 K34 20 1.Ox107 K35 4 1.Ox107 K36 3 1.Ox107 2.9x107 3.3x107 3.3x106 4.Ox106 1.3x107 1.Ox108 2.Ox108 1.3x108 1.1x105 1.1x105 4.Ox105 5.Ox105 2.5x106 3.3x106

a)Redox potentials (E) and association constants (K) are described _{in V and L/mol} _units, respectively.

(18)

-1000 -1200 -1400 -1600 -1800 -2000 -2200

E/ mVvs. Fc/Fc+

Fig.2-2-3 Observed _and _simulated _{cyclic voltammograms} _{of 1.0 mmol/L}

AQ in the absence and the presence ofO.01, 0.1, 1 mo1/L ME 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 0.1 mouL

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 2-2-2. .

(19)

i L3E=f[..T:t3at7T=SLI';J6/:I:l'kJjE2*K fly-JjEE=.$ 9 _{/ -)L} _{a)i'1'l)ji:t=J.f1/a}AQ a) '6/J(ji::;].--(T5;[IJtI6U)tI.1Tl)ii:7oD 7 _T.1 )L _7:rf41ft3 1U) _AQ _{a)./dI'.-i''-TilJl-S!g7E=J3}i_)T[1-:l'kT/3I i i)fve

8 _{[29]. =0)iB!L57oT]7} _71)VtiAQ _{0)#EEki&#ifi1,} }9/-)VO).lB!Eit=o)*i&

#L,, AQ 0)iB!E5bST3}t=/JlS U)tft=BEjiT8. fEet= =0)#Eg7oT] 7 _71)VO)#tH

-A-fi:fLY_A-iT.

=e)@Sj*fEj&jiFSAti-Fie8=j%1j= 5 k, 1 _{3iife) AQ} i _nLifO)} _{9 ) -)V?3:} O

/J(i:;[lt;l5-L4<(HD)E=A:())r-2l'ka n?a /J(ji:.-#.-.:I_TS-l]t(1=(AQ-(HD)n)a)5T''-1'@.i1-CT.2i1I i i)iTti ,

%m%)no)@Sj*4=BRE&% K1-KD i L,Tie L,7=.

AQ + HD S _AQ-HD KI

AQ-HD + HD 0 _AQ-(HD)2 K2

n 5JLia)

/J(i!i-(l[;-i)-.I1<i /)(;J,.;.-,S.Jf.fTSJf;[4<*JrfJ'k1 /Ji,i.(i ti(3)I-C7?-T{i a1/a.

AQ-(HD)n-1 + HD S _AQ-(HD)n Kn

a: f=, i+-TT'lf9:I_ii-Cti.]lTt!)igi iF fIB.--lJiE&TI{1I i 7P7 i?3.

[AQ-HD] = K1[AQ] [HD]

[AQ-(HD)2] = K2[AQ-HD] [HD] = KIK2[AQ] [HD]2

(3)

f'1f?I, n 5ji+a)7J(*i:-fll;lj-,[1<re)r-ZJ'ka a1Yu _{7)(i,:.-a'':.fT-.}(_T3[tE[6_U).;'T3)iE(i(6)I-C7:I,T;a 41/3.

[AQ-(HD)n] =

Kn[AQ-(HD)n-1] [HD] =

KIK2...Kn[AQ][HD]n (6)

g68=, #)>0)&'i5WB%EE% 1 tT8t,

[AQ] + _[AQ-HD] + _[AQ-(HD)2] +... + _[AQ-(HD)D]

=

[AQ](1 + _K1[HD] + _KIK2[HD]2 + -.

+ _{KIK2...Kn[HD]n)} = ₁ (7)

(7)iC8='j{Sm8 _ck5 t=, _{5FyjE&t7k/iFej$1ASj*iB%EgTiE1=} tbS7hf8. I _=7?(7)

ie*0) 1 + _K1[HD] _{+KIK2[HD]2+...} _{+KIK2...KD[HD]D=} a tT8 i,

n5iijlo)7k#Rj$

l#Sj*8=ck O _{Jr3hESm87k##E%@Ej*0)i&Ei[AQ(HD)D],r.} ti(8)-(ll)ieTiiS n, _7j(

i:i-()I;lj.(1<tI!lri-liE[I-ID]7:I,Tl-II i !Ji7t5 /3.

(20)

[AQ-HD] pr. = _K1 [HD] /a [AQ-(HD)2] pr. = _KIK2 [HD]2 /a [AQ-(HD)D]Pr. = KIK2...KD[HD]n /_a (9) (10) (ll) liu-_

a).;-r?,T/i-C7htL. AQ )i LRIIU)_{/J'J,::;I:.li-}{T S-ilt(6a) i )L5ji;l['t':-fur

7)ia::;3:..,I(T5;E]t(1<:(:-.I,kf7T7;..a i

/I(i.-fll;l7--[6U).I'T3)iE-rEt:{{TI _{i !)i7.-i}/a. _Fig.2-2-4 _{tit-I,ri.[ulE=}_i ₉ _/

-)L_U)t'f51ig7i7I['-1H!Skf

tE(Tt{iL iBlf.Ii-Ih(I/iM(j!i-a.ri:_TSIrfI1<U)i)L5;h''ti7=r={{L f= 9tt-)7 Tt. _AQ _{U)fr.i'iJ,Till(-TiEV)ih[I1}

･r%,7=*>9-}*)V, 9h117=j->0)tfO) 3#*qk?U)Tj%L,f=bO)7?ZB8.

->= i L,-->3 >0)#EB%75) 6, AQ i2jtj*7?b87=*>9-}*)Vt9)17=*>

8=BU)T} 9 ) _{-)VbS*A8=7k/*#E%@Ej*%3T3BR18} I tbS>j%gm7T=bSh, Fig.2-2-4 0)

9119 7 _7JltLi 9 /

-)LU)tI]l'i-Jiga)l'.Y.'Ju[TC _[l'---3 I _IL::;:)(U)_/I(A.:;3.I.:rTS-[r;[4<*JT-2J)kT?3I i i)ifn

lil-inF.)t=;iJ,.E*l]ka1/a. _AQ _{i)iJ.TiI-.rT-}_{fur;.tll',:LRlyu}_t2_tt_X ₉ /

-)L!)Sll_tf'T3)ii:rebT3 I b 4;< u)}](

i!,1:-#.I...&SLI';I4<7:yI-L:.I)kL I L)/u I i 7yu[T!_1nJ.ILL.T.i, i T=fL8.-V)tllT3)itv)i 9 / -)L 7i.-)I;.-(l=a tt

f=P$0) AQ 0)&4Ei2jt} I)=x1'i> i:fig.FJ18 I tb57>%8. 5T]kij:A,Fig.2-2-3 T} 9

)-)V% 1 _{mo1/L##Siff=t%a)} CV _iL 2 {jtR;BBC)@1E32jti&%j(%< , 1 gRPFEjbB

0)@1ki2jti&%/jig < df-}j1-I 7P;)7 t, Siff=b3>, Fig.2-2-4 A) 6 7 T)_-0) AQ Bj=V)

1:1 @Sj*b)67=*>9-}*)VO) 1:1, _{1:2@Sj*&Jt3BEL,,} _9)17=j-> i:5, _1:6@Ej*

fly/Iir).qT?3I t!)(JII!P]TIE.T.i?a.

/>BTU)->= i L

--ia >T.I.i * 9 / _{-)LU)[L::;i'T!)igf-Jl:i)iRE=J3L}_ITb. 1:6 5;[rfJ1<cE()_['.I:;

;1(a)5;['fl1<Jrfr)k(=r!BLT(i-> i i L

--i a i _U)a.[.:T<E=.r;l3?T)i!tifj:< , 1:7 I).I-_U)S[';I4<tin12

[E.iGijtfJJI _{7:LJJ' t1}!!T.uJrl173I t!)Sit i?a. a:7T=. AQ SEE)tI1<U)S(I;[1<!I=),.GJif2!{Ii7)i

Bll(k[1<u)S-[flt(1_('r--_r)kJJi]/;]&Kct ()_S))(-iii_I _i/)Sh. _c,v _!Ji7f

->1jl J 7I-> 7 I, L,f=T5;1Tt)(retb

?a _i-,t'j-,i_tt)ai/a. iT=. _I.::)-i_{ltI.T3Jiga'i)iRretL}_{i tl}l=7S-)tjlJ(7t->7 _I-1/3 I t!);7,)t!I]J

$41?u7V1. _{J[-1i;(;I:a)->}7 _{1- AELi} _Kt i 9 / _{-)LU)ti)Tlflljf(I(!(().:I/3}_{i-'Lr)-it3a1/a.}

(21)

0 1 0.8 0.6 0.4 0.2 0 0 1 0.8 0.6 0.4 0.2 0 0 1 0.8 0.6 C-.4 0.2 0 -4 -3 -2 -i 0 logm4eOH] -4 -3 -2 -1 0 1ogPvleO H] -4 -3 -2 -I 0 logP4eOH]

Fig.2-2-4 Molar fraction distribution _{of the} _various _species formed by

the _association _of AQ (up),AQ. (midle) and AQ2- (under) with ME in

MeCN. The diagram was traced _using the _equilibrium constant listed in

(22)

'#5=L^!T]l_{tITFI1:JBu)7J(a.::(l1/J14<((--[f-:fE=J3tlyu}L T{ty 9 7l i JJ=7:i:A)P]TF.fJ7.

*i=} T,#->7I)-)V&##giff=t50) CV _0)->=1V-->5 _>%17?f=. _i

I-+ _->7 I _{/ -)L} ii9 1 7^H E=5iili:IiSa1,/)(i.J,:.-[lJ;lj-(67:rTr:,iti'nrA:7?-)I,--().:Silf=i fU)

AQ 0) CV ti1 [RRf 2 iE1#&&j%T@4E32jti&i:j{L,T=. =0)7T=b, AQ 7=*>9

->7))LU)ByEiB)tJ.-i[1JI-_?bt/l',i:;;I:.I.--(T5;[If[4<7=r)ril),tT/aI i (I

cE())(i < 7Jf->tj:/ 7+-i 7

T-UTU)?T=t#iRTJSn8. 3:f=7I / _-)V#,ti} _{9 ) -)Vi: O} b3}jlo)31j*iAiBbShj(

i ilf=S). 1?U)/I(iL:-#.I,..nllr1= 3 5ii+lJJ-_a)7 I _/

-)L7Ph/I/A,:;3:.I..-JFF}*Jr.Zr)k1/ai

ii%A#< , Scheme 2-3-1 8=j%1j= 5 fIBj( 1:4 @Ej*i:A3BET8jiFE;i i)=Xi"7R-i:

*L&L,T, ->S IV-->3 >%fi?f=. %0)#fB%, Table2-3-2 kj%T^o9}-9-a

A]U)f=tf, Fig.2-3-3 kitL,7T=ck5 k, _->= 1 V-->3 >L@t9;iF,rJl&tij=U)-&%j%

L,f=. =0)I tb) 6, Scheme 2-3-1 _{0)jiFS}h=xt'i>} i Fig.2-3-1 8=j%1%@Lbi2jt

I.:i[1'I-_J3_cEVt5.l'fI4</I--_I)hi:ti&7yLE;I-j7:.A Yu _I _{i 7Ph71{a 4}1f=.

Table 2-3-2 _{0)7k*f*E%@Si*0)&4Ei2jtfE1%} 8=j{ i mf= a: 5 8=, 7k/*#5%@$4* %1E3BR

I?a/I(A.i-;fit;I)--[62*7yu[I1''.'i/J= i;CL.l. _=J,Tilla _{a)F2IEiB;-}-LJ.Tifll!-_ti}

-'r]ijiu a)fa 1E=3Cjh

<. 3:f=, _{@1Ei2jt%15EO)->7} _{LO)igL5bSh}9)-)VO)tf8=tb<Tj(f<} , 5:f=yf

HBgT,b8f=b, _{i 9 ) -)VO)} tfi=%iFlrJEnf=j= 5 _{fEq39f3:@1Ei2jti&0)*#Gfaj{}

-}jlJI 7h'->7 hbSh&iP.TJTffab)?T=t%A 6n8. 3:f=, 7j</*#S%@Ej*4:BE%%tr@

IEi2Jt } }]I _7:il/)i_{ITIjgtj:)j1,i;Ttb}/a _I _i _{i)I.lI!J(YLI-7?-c*}/a.

(23)

AQ

tK1

1 AQ-MP

lK1

2 -PP)2

tK1

3 -PP)3 E10 I , Ell I , E12 E13 E14

ATT:;

1 A

Qtt-;;

AQ.--Oap)2

TIK2

3 AQ' --Oap)3

TtK2

4 AQ' --Oap)4 E20 E21 E22 E23 E24

AQ2-TtK3

1 AQ2--MP

TtK3

2 AQ2--pp)2

TtK3

3 AQ2--pp)3

TIK3

4 AQ2--pp)4

Scheme 2-3-1 Equilibria involving two-step _one-electron transfer _and

(24)

Table 2-3-2 Estimated hydrogen-bonded _complex formation _constant

and electrochemical parameters giving the best fit simulated

Calculated Parameters _{of Redox} Reaction

EO a cL ks E10 _-1.32 Ell _-1.25 E12 _-1.18 E13 _-1.05 E14 -0.97 E20 _-1.85 E21 _-1.60 E22 _-1.36 E23 _-1.22 E24 _-1.02 0.5 0.15 0.5 0.1 0.5 0.1 0.5 0.1 0.5 0.1 0.5 0.05 0.5 0.1 0.5 0.1 0.5 0.1 0.5 0.1

Calculated Parameters _{of Equilibrium} Reaction

Keg a H kb Kl1 5 1.Ox107 Kl2 3 1.Ox107 K13 0.01 1.Ox107 K14 0.005 1.Ox107 K21 55 1.Ox107 K22 40 1.Ox107 K23 2 1.Ox107 K24 0.1 1.Ox107 K31 9x105 1.Ox107 K32 5x105 1.Ox107 K33 400 1.Ox107 K34 300 1.Ox107 2.Ox106 3.3x106 1.Ox109 2.Ox109 1.8x105 2.5x105 5.Ox106 1.Ox108 ll 20 2.5x104 3.3x104

a)Redox potentials (E) and association constants (K) are described in V and L/mol units, re _sp e_ctively.

(25)

-800 -1000 -1200 -1400 -1600 -1800 -2000 -2200

E/ _mV vs. Fc/Fc+

Fig.2-3-3 Observed _and _simulated _cyclic _{voltammograms} _of 1.0

mmo1/LAG in the absence and the presence ofO.5, 5, 50 mmo1/L MP at a

scan _rate _{of 0.7} V/s. The _observed _{voltammograms} denoted by lines

were _recorded _with a _GC _electrode _(qFl

mm) in MECN containing 0.1

molJL TPAP, and were background-corrected. See _experimental _section

in the text for details. The parameters used to obtain the simulated

(26)

f'J[J-L^ilt)-I,.-J1-.:A(I. -i i i L,- _-i

_q > 7? 7-tJf:tla1T=SIrfI4<!-I:I)qJiE&7hLla/I(j!.:;a,T..'fTS-Ltfl1<U)tIJlrifiE

7oU7 _{71)V&1fBEL,7T=.} #EHiEtiB6H5tRf,%7?A O , Table 2-3-2 0)L6&jn)T,

Fig.2-3-4 t=f'T31ig7'ltj7 _T 1 )Lfr'T-:Lf=. Fig.2-3-4 fJI_{L1/J(jL:-[ll;}_{()I-IHJSlr{fJl.iliE)iRT.S)3?}

< _{a)/J(i:,:.-a.li-n$1;L4;}_7=r/I:_l'kLL I i1/u _I _{i I)S7!T!_[nJ,'I!7?}_5, _{9 1} _7L-I_I V) CV _{a)T!J-:fTx7i7-.;i;aU)1?3}

I tb3hTf8. eUktihFig.2-3-3T, i t,#->7I)-)V& 5 _{mmouLiSbDL,f=t%0)}

CV _ti3i&B b57Ptj- T{11Ja? 7T=b3>,iB!LibHog(0.005) =

-2.3 0)iB!E57o[]7 7-I )V75)

6%A8t, 71)-0)AQ A)67=j->9-}h)VO)7T)-3:f=ti 1:i _@Ej*%4:j&L,

9h117=j->0) 1:2, 1:3, 1:4 _{SSj*&fEBET8=tb%ib)8.} %0)7T=b, _-i&B3:7?

ti t2 i /tJtt/J<fr:;a,I.--I_TS['1t(1<7=r)r-iJ)kL T i1_{fl i})_{7Dt. I} U) _'f[r='.id3E=_Ttti_{Xci!TiU)/J{i:;;.ri-}_{(_TSL[tH6}_>=y

lr3BE18=tb)6, 7)b- T<1&&j%L,f=tBf#Tf8. 3:7T=, Fig.2-3-3T} I,#->7

I /

-)LfLY;A :[Tr_:a-)50 mmo1/IJ i;TU)lli fU) CV ti -i:zrLP!.?=Jt=E+f3P)fly,Tl-T=ti)i7Jin2i

mT=b3>, iB!&bHog(o.o5) =

-1.3 0)iB%E57oD7 71)Vb16, AQ 0)7 1)-3:7T=ti 1:1 @%

jib)67=*>9-}h)VO) 1:1, _1:2@Si*%#T, 9h'17=*>0) 1:3, _1:4@Sj*%fEBk

18=tbS3iib18. 3:f=, '4=BEEn89'17=*>0)i5tjut"bu:4 @$4*7rlb O,

-i&a _{a)@1Ei2jtiE15Et} i2tihR i;L&%j% LTU)8 I tbSlable 2-3-2 ₇₅₁63ii7518_ck5 8=,

-ExrLP!,?_I[Td+434U)7itI7)iTiik--[J:Tl=fj:?T il7u i '5-RLL14i?a.

917o I t917oIO)i5U)tL 917oII7?ti%0)#U)7oT] I,_>BtSJr%b)6, IfEiB&

Tt i)_{F:,I)-:)(a)7J(;i:;3:.Ii-(-}5;Iff(1<7;.-)rfl)k}L. + / > _{V)tlq'ifEi2JtJFEfltI-_}_;=Y)(i < _7F_{->tjl I} 7h-> 7

T-gif8 I tTb8. %0)#5Bt, 91 _7oII 0) CV _{7?1bkJ*#%SEj*fEBRb3>j(fU)FIB,}

Jjt_;I'L:R']t=/I(jr3:#rf.--{TS-f'1t[1=?V1.-_I)qa a1yu. _{L f=}_{/Jib? I.} _{iu!-S'r,'En'JfiEi'T31iEf!(-(l{iJl:i)iliili!T.TJ}_{i 3}₁_Th.

#=i&0)7F-}jlJI 7L'->7 hbS%ifUJSn8 tU)5 j= O , 7Nb- f{j3:iEfEO%? 7T=i&bS&

7lTJJ$41?a. #A:ill-iLT. /J(i:;#[Ji-:_TS-Ef[6[I.-.I)n=n'--:) # L i)7F-)1jl_I(1-> 7 I-!)ihBiilTJJSa1. ---FiL[S!-,?=1JFE-I-iCE=_4f!?ai-15.iLtLa1/u. I U)cE j (I LJ.--Ti+u U)iB)tJGf1[I-j)i-JFE-I-ti_It]rI

i_1(kfLY7T1-L.

---rlr;i-,?LJFi;-f)i1,i(7Ji'tg-i/a I t7)S19 1 -iI i 9 1 7eI

*LY}JnkYiT/u.TL'__!5LTT-:[iiT-/T#t5#7fZB8t%k 6m, 7oD I,>13tSJl%o)*go)iBLFR8=j=?Tti91 7o I t91 7oI 0)

m a)iJ[:_'F:r7:r_7RTl-ii.(lL7PIb/u _I _{i i) ll]![nJ,'f-Tt}_i /a.

(27)

0 1 0.8 0.6 0.4 0.2 0 0 1 0.8 0.6 0.4 0,2 0 0 1 0.8 0.6 0.4 0.2 0 -5 -4 -3 -2 -1 0 log_P4P] -5 -4 -3 -2 -1 0 logP4P] -5 -4 -3 -2 -1 0 logPIP]

Fig.2-3-4 Molar fraction _of the _various _species formed by the

association ofAQ (up),AQ- (middle) and AQ2- (under) with methoxyphenol

in MeCN. The diagram Was _traced _using _the _equilibrium _constant listed

(28)

0 1 0.8 0.6 0.4 0.2 0 0 1 0.8 0.6 0.4 0.2 0 0 1 0.8 0.6 0A 0.2 0 -5 -4 -3 -2 -1 0 1ogP4P] -5 -4 -3 -2 -1 0 logD4P] -5 -4 -3 -2 -1 0 1ogD4P]

Fig.2-3-4 Molar fraction _of the _various _species formed by the

association _ofAQ (up),AQ- (middle) and AQ2- (under) with methoxyphenol

in MeCN. The diagram was _traced _using _the _equilibrium _constant listed

in Table 2-3-2.

(29)

hJ15tLgl^gJ-_.)q;.i_ul(i;(lr;I-i-[1<(J.:Tr-:-rI(=J3t+?3L T{I) /}7lf h I _{7:LhU)P].'['lt-rr}

9 1 7:liltiB1111:_lita)_i)qu_{)JR:Jri!tfT-F%itJtn;nJitiE}E U) J] )L# i,_{B<iti!l'iiL3FJV!}i_lfri+rT&_i)I_iLGi)f[7T;[

r)∼;g a t7= 7 I / _-)LIE.:fifur-)rJia ifT= i f7:tb ().

lL::)-i)lTiJii:U)7J(a.i-;(lr;.FJ16 7:r-lf;--(iT:a ifT= i

i. ni9i[EiTU)17b

-T<Ii fI -3 f= 1l-TT[3CfICV iT!fLYiF1I i i)i3-.'J-:TTxn'.JTtb/a. :L-U)f=i5.

9 1 7'llla:veU)cE -jt=. _AQ _{i)ih7J(i:;3:.I,.-{q5;[tfI1<,i.I)rfr'k}L fU)B4iIEiS;-i-tJ.lil.I/-_a)-i7 I-7El

t.+7?ti[il;aTyre-Eilt._/J(a,:.-IIJ;lJ--[1<1J't3AQ ^7''D I-> /Jiti$4U)T/urdJL;f A I _{7:i:1r:.t'j.I.tij:}

1/uJe.-.AtiJi135?a._{I,-EFg{.TJf:Ill:t=ct}_/uiB}-Lt 7'lD 1->f34U)Ji),i;*LY..∼ _>.j# / i _tJR'-JLiIJt

n{i*JIJJE=File.2-4-1 t='l-1-LT=. =U)J= j E=7rD rti,fSJ;-J)a)figE=J.:ri/[.-i7JirTIT-IT$41?ai )I

=x1'i>%%L&L. Scheme 2-4-2 _{8=itT}*=xt'i>T->=} i V-->3 >%fi?f=. 7o(]

T,>j3#MilJL-tTtti7l-D I-i 1 _5jiji/)i_AQ _^f$4!J)1/a i AQ U)JFE[[.-i/)uJFti-I-r]1frT$41 /a

7T=b, AQ 7=*>9-}h)VTti 1 3iifO)7oD h>, AQ 9}17=*>Tlti 2 Life)

7rlD I->!)iti3P)1/u I t7)i _{lITfJtETtb/a.}7-Ilo I,>!JiiSJ;'))LT= AQ a)}J(a,3;;I:.I7-Ri}11,tL

A )L.7f:I)L);I;-7P)/J(r111-HE-Jli _'Ji'[ET?aT=i5. _{/I(i!,:.-#,[.:I_TfJtE}i:*t-jI i 7hL-T,illJJa a1/u. ljJ=

a)3Rjff1#&%L&L,T Scheme 2-4-2 8=j%1LiFS} h=Xiu7R%fB* L,I->S i V--> 3

>%1??f=t=b, Table.2-4-3 _{8=j%1/i9}-9-%jn)7T=t%,} Fig.2-4-4 _kj%T

ck5 k->= 1 V-->3 >Lit9si,FJH5tickU)-xq%itL,f=. %0)7T=b, =0)7o(] I->#

@-))*L7T_:JTLnB;2_IEiEi7-tJi

I,i;iRV)i J]I 7,Ill,i i U)rlJifEi3)tJ,Tif1.I-_J3_LtLntS-l.;f6/[iT)q;E&7Ph&'-j

Teb8 t#UWLf=.

91 _{7oIII7?tL 7k*f13fSi*0)7oT]} L >bS> AQ 0)A)Vji=)V2S^##L,, t=S/ >

j->hJ))L7h _{L1/1 1 T{ D+} / _{>7iyI/I:_I),qT/JLZ).i;7Ptlkf/a}I t7yW)JL17httj: (). =U)I i

bSh91 _{7oHI%3iixTg18iE2fBlkfE8} t%k6mf=. g 68=, 9-1 7oHO) CV _bS>7<q

39i&tfa?flo)tL 7oD h >AER#jiFS75S>if3gfa?f=f=b t*A 6mf=. 3:7T=91 7o I,

I , IIIO)1ilq:6m7T=/i9}-9-A) 6, 7oD I,>13t$8Eb3hS < f3:8i5t"7j(,*#%SEbS>%

< fg O , Jr3BRSm87k/*#E%@$4*0)@4E32jt%1ktij(i < 7o9X8=->7 I, L,, 7oT] h

i flI;-ij.ll:_T'JLE7Pt+/ i _{a)I.Ti+iSdiJ)}E=)(i < ;;:3-I;tlr,tiL,I il/3 _I _i

(30)

.q2

1 H I /

i

P I

oio

e-i

.g!

I I I

.

l l l 0 I /

oio

i

0

oio

.

L [ . /

oio

_.q2

A

0 / H

oho-BQ-BA2 BQl --BA2 HBQ'-BA HBQ--BA H2BQ

Fig.2-4-1 Reduction _mechanism for _{proton-coupled} _electron transfer in the

hydrogen-bonded _complexes _of _BQ _with BA.

(31)

K12

_HAG

I K25 K2

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

(32)

Table.2-4-3 Estimated hydrogen-bonded _complex formation _constant

and electrochemical parameters givingthe best fit simulated

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 0.15 0.5 0.15 0.5 0.05 0.5 0.1 0.5 0.15 0.5 0.15 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

(33)

-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

(34)

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.fillli:'t'}-RLLla1/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;--I_TSZ)tI1<_a).ill-ili7:y+ / i _ti'T2_lit-,

/i(,i:.-(lr;li-L4<tilTl)jH3cELRIS-[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[[fI6a)

tlllrl)igti/J(jL:-[lf;1j-[1=f'T3-)igJ3 A:V1S-rLfl6!I:_))ktJiiitiFx7:t7]-{1I i 7V7t i?3.

(35)

[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(]ih_Li5iHJ1/aJ= j (I. _7)(a,3;I)[;_{I)--JrJI=j)STi)q!L}_IT=&b l_{lTJr:I-._u)+}/ > i i_)5;I.fl67:r/fiJ)E

L,f=. _{i L3}t= AQ _{-/)iYLilg([TL;I.'I:t=J=}()_iEi)tgalYu 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 L1}

7J(i;fit;lj--(1<7blf_T_-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 )kLR11:1 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]]..1i_E=7-ltj}T,>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+i7JiEL. f JJI _{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 I

-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)

(36)

BA U)iJq;.i_{1/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[Ti11a _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.}

(37)

0 i 0.8 0.6 0A 0.2 O 0 1 0.8 0.6 0.4 0.2 0 0 1 0.8 0.6 0A 0.2 0 -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

(38)

:1Jli7T_fi;7_/J(ji-Ill;-i-)-.[6-(-i-(i-TE=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-olvti _{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?aI _{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)uJJHilB'.)tT/a /)(i,i#.I,--(TU)

I;;u-ntfLY-):-uruf=SbE=tLi['Ill&(1)*J7)i_{IT,t'j-I/S;fT/a}I i ti1,-Sam)T19/3. I =7?, iu-LJr-Ti

[i /)irCh.'f-!n'.J7Ti1'-i'llT-II))T. A /a _I _i fI-,t'3._I..i:i:_L. I,jJti_{liH}tJiEI;I;i:J'^J32ihtJ.=B}_I;.I:E=_*fT /a

/)(i; ;I:if...i-TU)iUunt_{7:r,ii'6.;A)1i71}_7Ji,i.(iE=_{8i, I4 1f14}i'a'1i_{liFlre.gil'kT}/u ₇ _I _A-_i _-)_->1_-A_)LU) j _-)1J]

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

%iEiELJ2R18 _ietfbS>4=i;a.

)JLf.Julia.:-f._BTA/IJ--_-jE=zBT= (). rwTJL:_a)J[Ti1'-1Ji-fig.frlt'Lril-)iEJ=< _=1iL , 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.--I_}5;Lit[∼r5)).k

E=

ct7JTULiCI -+,)L-i=-,Af[E7hLL/J(i!.i3:[Ii-{3.a),;'juLILa.i-JYi.;-rli7L f=. -1=5hiLIULihl-I--^i-1:Tli.;-[.-^* a)rLtt)lu.3IEV)f=i5,AQJ= ()_{i_'.)}Lf_:[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'::,-il_(=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]ftTi_U)[IULjB7:y_{Jr:!-tikret&.'i-V1.}-I-4Ii).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

l_ti_{a"i:Jji:[EU)51;ul1!!Ji)(i}i).

(39)

I

'J::

::

+} JJJ JJ /JL J Bq-ME4

PJ.I

IJ

I:,

+

i-4J/Jt-Ji--i,

BQ-BA + JJ} Jri-J J J i + J. }JJJJ }JJJ} J BQ'-.PH: } J J} I-Jt} J e

:J:

1 + J J4 _J + } I }q BQl--pH

I:.J'.:JJ

J + 0

:::

J i JJ JJ i', .)

.,S

a.I.

Bq,ME2 i

･jJ::J'J

}4 J + ) )i J } Bq-PH2

J-:

:8J

J..,::.J

JJ:J,

,9J,

_,i.

8Q' --ME4 I } v-4. }JJ J+ H8Q I. tu a) Chat.ge :0 I }JJJJ I }J.JJ + BQ .I

:I:I:

.+ +

JJ:;::

Bq.PH b) Char.a,qe: -I

J}J

+ JJJJJ J.JIJ} +

}:

BQy--ME2 }+ }JJJJ .J

)i-:-a-J

JL-, HBQ + J + } } JJ .-iJJ ? J J + }-1J + BQl-.I)A + J-. J.1J }JJIJJ +

(40)

c) Charge :-2 + J.J.J J-JJ-+ BQ:I JJi_JJ. J.JI.J JJJIJJ +

JS.

J.4.}

Ji{

:i.. .I JJJJJ JJ.. A-} + +A J.J.J JJI.JJ + J J-J.rlJ JI + J J. 44JJ 44J-J +.J. J I.-44J .J 8Q2-,ME2 BQ2-.ME. BQ'-.Pt{ Bq2-.pH: } JJI

JJI-JJfJ:.

+J JJJJ} JJ.JJ + 8Q2--BA J+ J.JJIJ JJJ-JJ + HBQ-J JJ JJ JJ JJ J+ +J -.. +I + t7ESQ_A-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.

(41)

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

(42)

(a) O)) (kJ 1110l.1)

C

+

∼

0

+

Jr_

_5iE

-400 (kJ mo1'l) I-?00 ･iOO ･600

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

!

+

HOMO _HOHO ....-.ll_ H OL(O

∼

･'m 'l ''''TUEd !TTT7T:...l' I BQ Zi_Q-1ZE I a Q-1(E4 a q-PH aQ-PH= B Q-BA

LET....,

∼

+ LuhSL.""Li2aii...-..._... e2ZZ2_J HOMO -I... ∼ 4∼

d3?

+ - J-+ qLW undo LT!E LTt6f6l..._ 1 I 1 ∼.B2E9...S9Zia...i-.--.S9q ･.P..._qi2ALn I LE2E2.II... I-''.. 't I I 't.:'iS2Zi9I ''... SOZW HT='''"''';

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

(43)

(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

(44)

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.

(45)

Fig.2-5-3/)1 _LI_{JFEqg:/rTi[.'I:}E=

cE()iE!>-a7:rJ1.ti-,I.-TJlli)S1-.T.-Aa 41T=BQU)'fULin-I-I,)L

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U)8 I tbSh3iib)8. 3:f=Table 2-5-4VLj%gm8 ASCFO)L6tL F17j(/*#E%@$4*Tti

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7>->7 I,L,TU)8 I tbS>g#7?%8. g$8=#B,S@o)*B%, 7oT] I,_{>b3h##L,7T=-ES}

#) >*^1 fthT]#)>0)%3EI*)LS-b3h*%<bR/j>LTU)8. Lb)L,, _-ES#)

>&V)ll Tthf]#/ >0)ASCFbS>7iP.TJL7T=ck5fEL&i:j%LTU)fab). =niL 7oU I,

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cE()i3

(46)

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fly

;I;-lrTJtPL,. I a)'[ld-ffSJ3-))7:rj > I-u

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7iTI.iLJt3*T=fyi)tiS < [30]. 1'JT)7_&5T

k'-CtlBli[Ei2jtJ[:(:_7:r-,1tTI i 7h_{LIJ.-E'x-([EJ1;.I-'U))Jiu!J1',TliLElilfiry)f';r}i L TJIJil_t131?a 7 I D i=> fLYAikf.iTfiL,T=f9-lJiJ[31]. 7nL 7

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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

Title