2 + 4e- + 4 + hν 2 2 1
2
20 J. Am. Chem. oc. Angew. Chem. Int. Ed. umber of Papers 15 10 5 0 1998 1999 2000 2001 2002 2003 Year : J. Am. Chem. oc. (Trost, B. M.; tanford University, UA) 3
π 1/2 k ET = V 2 ( G 0 ET + λ) 2 exp (1) λ k B T h 4 λk B T 4
(a) (b) mall λ Long-lived C tate * e D A G 0 C Charge eparation (C) e D A k C λ small λ large fast C hν G 0 CR Charge Recombination (CR) 1 lo g(k E T/s ) k CR slow CR D A G 0 C G 0 CR G 0 ET / ev λ π 0 5
l ogk 11 10 9 e t, M 12 11 10 9 12 10 13 13 9 14 7 15 6 8 16 8 7 15 14 11 6 3 7 16 5 5 3 4 17 6 4 1 2 2 5 18 18 1 s 1 0.2 0 0.2 0.4 0.6 0.8 1.0 G 0 et, ev 6
Me Me Me 2 C M Me Et Me Me Me M Me Me 2 C Et Me Me Me Et M Me Me Me 2 C M = Zn (5, ZnCh C 60 ) M = Zn (1, ZnCh C 60 ) = 2 (3, 2 Ch C 60 ) 12 10 8 3 2 6 4 5 1 M = Zn (2, ZnPor C 60 ) = 2 (4, 2 Por C 60 ) CR Me Me Me Me 2 C Me Et M Me l ogk 6 C 4 E Tor k BE T,s 1 5 1 2 0 M = 2 (6, 2 BCh C 60 ) G 0 ET or G 0 BET, ev 0.4 0.8 1.2 1.6 7
(a) Me Me Me Me 2 C Zn Me exyl Et τ = 230 µs (298 K) Me Angew. Chem., Int. Ed., 2004, 45, 853 (b) Zn = C τ = 0.77 µs (298 K) JAC, 2001,, 2607 Me (c) Zn τ = 330 µs (278 K) Me (d) Zn ZnPQ AuPQ + τ = 10 µs (298 K) Au rg. Lett. 2003, 5, 2719 JAC, 2003, 125, 14984 8
(a) (3) (2) (1) Fe C Zn C C C 3 (4) τ = 0.38 s Fc-ZnP- 2 P-C 60 = 3,5-di-t-butylphenyl (b) hν hν hν e e Fe C Zn Zn Zn C C 3 τ = 0.53 s Fc-(ZnP) 3 -C 60 9
1 * Fc- ZnP - 2 P-C 60 (2.04 ev) k E Fc-ZnP- 1 2 P * -C 60 (1.89 ev) k ET(C1) Fc-ZnP- 2 P + -C 60 (1.63 ev) k ET(C1) Fc-ZnP + - 2 P-C 60 hν k ET(CR1) (1.34 ev) k ET(C2) Fc + -ZnP- 2 P-C 60 hν k ET(CR2) (1.11 ev) k ET(CR3) 0.4 s Fc-ZnP- 2 P-C 60 10
(C 2 ) n n = 3, 6, 10 Zn hν k CR = ~10 6 s 1 Control of a tructural caffold Control of Redox Reactivity of Quinone µ 11
12
λ λ Ph + Me λ = 0.34 ev Ph Me (AcrPh + ) (AcrPh ) EXP. 5 G 2.00 0.28 G 1.00 g = 2.0025 3.00 C 0.60 3 3.62 3.20 IM. J. Am. Chem. oc. 2001,123, 8459 msl = 0.22 G λ 13
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Ph-Q Me 3 Ph-AQ Ph-AQ aph-aq An-AQ aph- 1 (AQ) * (2.85 ev) hυ 0.34 ps aph- 3 (AQ) * 1.7 ps (2.45 ev) 71 s at 263 K in Frozen DM aph + -AQ (1.97 ev) aph-aq 15
Bz C 2 BA 0.57 V BA + ZnP-C 60 h ZnP + -C 60 0.71 V 0.67 V ZnP + - 2 P-C 60 0.67 V 0.67 V V + V 2+ 0.42 V C 6 13 + (Cl 4 ) 2 + C 6 13 = C = V 2+ nv 2+ Au n BA + V + Au n 2 PC 11 AuMPC BA + BA V 2+ 2 PC 11 AuMPC/V 2+ hν BA 2 P + C 11 AuMPC 1 11AuMPC/V 2+ 2 P * C V + 16
2 2 hν Acr -Mes + + + + 2 Acr + -Mes Acr + -Mes 2 + 2 2 + 2 2 17
TE e - e - n 2 TE: ptically Transparent Electrode e - e - e - e - hν e - e - I - / I 3 - Mes-Acr + -0.6 V Mes + -Acr + /(Mes-Acr + ) * Pt -0.2 V - C 60 /C 60-0.3 V Mes-Acr + /Mes-Acr CB 0 V VB hν 1.8 V C * - 60 /C 60 Enhanced Photocurrent by upramolecular Charge eparation hν 2.0 V Mes + -Acr + /Mes-Acr + 0.5 V I - 3 /I - n 2 vs E 18
e - n 2 e - e - hν TE e - I - / I 3 - e - Pt Acridinium Dye C 60 Ti 2 anoparticle TE: ptically Transparent Electrode 19
D 4 P 4 = 2 P-ref D 8 P 8 D 16 P 16 η 20
18 a IPCE, % 12 6 b d c 0 400 500 600 700 800 900 1000 Wavelength, nm 21
Primary Molecule econdary rganization C (C 2 ) n (n = 5, 11, 15) Toluene C 60 Au Tertiary rganization C11 2 PC15MPC (n=15) 2 PC11MPC (n=11) 2 PC5MPC (n=5) 300 nm C11 Quaternary rganization Au MeC/Tol = 3/1 ( 2 PCnMPC+C 60 ) m η 22
e - Pt e TE I - / I 3 - TE: ptically Transparent Electrode e - - Porphyrin C 60 Gold anoparticle e - hν 23
λ D 2 D + 2 D 2 D + 2 M n+ M n+ D + 2 D 2 M n+ D + 2 D + 2 M n+ 24
hν + Lewis acid hν f Lewis acid Me Me (2) 25
g = 2.0038 M n+ Fc Q ET Fc Q Fc + Q /M n+ First Example 6 G Fc + Q /c 3+ Fe + Fc-Q Angew. Chem. Int. Ed. 2002, 41, 620. (C 2 ) 5 ² msl = 0.35 G a(c) = 2.57 G c 3+ a(1) = 1.80 G 1.73 G 0.60 G 0.20 G 0.10 G a(3) = 0.70 G a(2) = 0.09 G a(2) = 0.04 G 26
c 3+ Ir(ppy) Q -nc 3+ 3 + [Ir(ppy) 3 ] + + -Q Q (a) Exp. (Q) 298 K (c) 203 K g = 2.0040 Exp. (n = 2, 3) g = 2.0040 (b) im. 5 G (d) 5 G im. c 3+ a(2c 3+ ) = 1.12 G c 3+ a(8) = 1.12 G Η msl = 0.90 G a(2c 3+ ) = 1.50 G a(c 3+ ) = 0.75 G c 3+ c 3+ c 3+ a(8) = 1.50 G Η msl = 0.75 G 27
Fc-Q Fe Fe Fc-Q Me + +M n+ Fe + +M n+ Fe Me M n+ M n+ Fc-(Me)Q 28
no alt hυ hυ in DM + + 2 P* Q 2 P + Q /( 4 + ) 2 in C 2 Cl 2 4 PF 6 no alt Bu 4PF 6 2 P + + + 2 P + + Q Q tabilization tabilization 2 P* Q 2 P + + Q + /Bu 4 29
π ππ 30
µ µ 1 ZnP*-Im 431 nm hν 2.5 ns (2.12 ev) 0.29 ns ZnP + -Im Š (1.33 ev) Zn ZnP-Im c 3+ nc 6 13 1.3 µs ZnP + -Im Š /c 3+ (0.80 ev) ZnP-Im [c 3+ ] = 1 mm 14 µs 31
Fc- 1 AQ* Fc- 1 AQ* Y(Tf) 3 < 500 fs < 500 fs Fe Fc-AQ hυ Fc + -AQ hυ Fc + -AQ Y(Tf) 3 Y(Tf) 3 12 ps 83 µs Fc-AQ Fc-AQ Y(Tf) 3 µ µ 32
µµ 33
2 2 2 + Cu(II)-Zn(II) 2 2 Cu(I)-Zn(II) Cu(I)-Zn(II) 2 2 34
3 1 1 2 2 35
C 2 Ph C 2 + M n+ Electron Transfer C 2 Ph C 2 (a) M n+ M n+ BA + Q 2M n+ (b) M n+ C 2 M n+ C 2 Ph C 2 Ph M n+ M n+ C 2 M n+ + C 2 M n+ C Ph BA Q M n+ BA + + M n+ g = 2.0031 2 C 2 Ph keto form tautomerization 2 C 2 Ph enol form 5 6 4 2 2 1 C 2 Ph g = 2.0031 4 5 D D 2 6 1 2 C 2 Ph 40 G msl = 1.8 G a (2) = 1.0 G a (4) = 53.0 G a (5) = 7.6 G a (6) = 1.8 G a (1) = 8.0 G a (C2Ph) = 7.4 G 40 G msl = 1.8 G a (2) = 1.0 G a (D4) = 8.1 G a (5) = 7.6 G a (6) = 1.8 G a (1) = 8.0 G a (C 2 Ph) = 7.4 G 36
C2 C 2 Ph BA e - C2 C 2 Ph Keto Form + + Ru(bpy) 3+ 3 C 2 C 2 + C 2 Ph Ru(bpy) 2+* C 2 Ph BA 3 BA + hν BA + 3 C C 2 Ph Pr i 2 + c 3+ ET without c 3+ 3 C 5 6 g = 2.0037 1 2 C 2 Ph Pr i 2 5G K 3 C C 2 Ph msl = 0.21 G c 3+ Pr i 2 k et Fe(Cp * ) 2 Fe(Cp * ) 2 + g = 2.0030 5 G 3 C c 3+ C 2 Ph 3 C 5 6 1 2 C 2 Ph Pr i 2 c 3+ Pr i 2 a (C 3 ) = 1.03 G a (2) = 0.90 G a (5) = 0.82 G a (6) = 1.11 G a (C 2 Ph) = 2.31 G a (1) = 2.63 G a (c) = 1.24 G 37
Bn 2 C C 2 + Bn [(BA) 2 ] Me (Acr + ) Bn + 2 C + Acr C 2 Bn DA Cleavage Bn C 2 2 + + + 2 2 BA + Bn (BA + ) C 2 38
(a) g // =2.010 75 G g = 2.005 (b) (BA) 2 + Acr + + Fe 4 Form II Form III 1 2 3 4 5 6 7 + + + + + + + + + + Form I 2 + 4 + Cat. 4 Fe 4 Fe Fe(C 5 4 Me) 2 2 2 + Catalyst p Co Co p DPA DPB DPX DPD 39
2Fe(C 5 5 ) 2 + + 2 2 Co(III) + Fe(C5 5) 2 2Fe(C 5 5 ) 2 + 4 + Co(III) + k et(1) Fe(C 5 5 ) 2 + Fe(C 5 Me 5 ) 2 Co(III) + 2 Co(IV) + 2 2 Co(II) Co(III) + r.d.s - bond cleavage Co(III) + + 2 + + Co(III) + Fe(C 5 5 ) 2 Fe(C 5 4 Me) 2 r.d.s 2 2 2 Co(III) + Co(III) + + Co(III) + 2 Fe(C 5 5 ) 2 Co(II) Fe(C 5 5 ) 2 + 40
R R 2 + 2 + 2 + 2 + + 2 2 Cat. Me Me Dehydrogenation p Co Co 2 + + 2R Me xygenation 41
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