Activation and Control of Electron-Transfer Reactions by Noncovalent Bond

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1

2 2 + 4e hν 2 2 1

3 2

4 20 J. Am. Chem. oc. Angew. Chem. Int. Ed. umber of Papers Year : J. Am. Chem. oc. (Trost, B. M.; tanford University, UA) 3

5 π 1/2 k ET = V 2 ( G 0 ET + λ) 2 exp (1) λ k B T h 4 λk B T 4

6 (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

7 l ogk e t, M s G 0 et, ev 6

8 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 ) 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 M = 2 (6, 2 BCh C 60 ) G 0 ET or G 0 BET, ev

9 (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,

10 (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

11 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 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

12 (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

13 12

14 λ λ Ph + Me λ = 0.34 ev Ph Me (AcrPh + ) (AcrPh ) EXP. 5 G G 1.00 g = C IM. J. Am. Chem. oc. 2001,123, 8459 msl = 0.22 G λ 13

15 14

16 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

17 Bz C 2 BA 0.57 V BA + ZnP-C 60 h ZnP + -C V 0.67 V ZnP P-C V 0.67 V V + V V C (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

18 2 2 hν Acr -Mes Acr + -Mes Acr + -Mes

19 TE e - e - n 2 TE: ptically Transparent Electrode e - e - e - e - hν e - e - I - / I 3 - Mes-Acr V Mes + -Acr + /(Mes-Acr + ) * Pt -0.2 V - C 60 /C 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 V I - 3 /I - n 2 vs E 18

20 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

21 D 4 P 4 = 2 P-ref D 8 P 8 D 16 P 16 η 20

22 18 a IPCE, % 12 6 b d c Wavelength, nm 21

23 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

24 e - Pt e TE I - / I 3 - TE: ptically Transparent Electrode e - - Porphyrin C 60 Gold anoparticle e - hν 23

25 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

26 hν + Lewis acid hν f Lewis acid Me Me (2) 25

27 g = 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

28 c 3+ Ir(ppy) Q -nc [Ir(ppy) 3 ] + + -Q Q (a) Exp. (Q) 298 K (c) 203 K g = Exp. (n = 2, 3) g = (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

29 Fc-Q Fe Fe Fc-Q Me + +M n+ Fe + +M n+ Fe Me M n+ M n+ Fc-(Me)Q 28

30 no alt hυ hυ in DM P* Q 2 P + Q /( 4 + ) 2 in C 2 Cl 2 4 PF 6 no alt Bu 4PF 6 2 P P + + Q Q tabilization tabilization 2 P* Q 2 P + + Q + /Bu 4 29

31 π ππ 30

32 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 µs ZnP + -Im Š /c 3+ (0.80 ev) ZnP-Im [c 3+ ] = 1 mm 14 µs 31

33 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

34 µµ 33

35 Cu(II)-Zn(II) 2 2 Cu(I)-Zn(II) Cu(I)-Zn(II)

36

37 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 = C 2 Ph keto form tautomerization 2 C 2 Ph enol form C 2 Ph g = D D 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

38 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 = 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 = G 3 C c 3+ C 2 Ph 3 C 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

39 Bn 2 C C 2 + Bn [(BA) 2 ] Me (Acr + ) Bn + 2 C + Acr C 2 Bn DA Cleavage Bn C BA + Bn (BA + ) C 2 38

40 (a) g // = G g = (b) (BA) 2 + Acr + + Fe 4 Form II Form III Form I Cat. 4 Fe 4 Fe Fe(C 5 4 Me) Catalyst p Co Co p DPA DPB DPX DPD 39

41 2Fe(C 5 5 ) Co(III) + Fe(C5 5) 2 2Fe(C 5 5 ) Co(III) + k et(1) Fe(C 5 5 ) 2 + Fe(C 5 Me 5 ) 2 Co(III) + 2 Co(IV) Co(II) Co(III) + r.d.s - bond cleavage Co(III) Co(III) + Fe(C 5 5 ) 2 Fe(C 5 4 Me) 2 r.d.s Co(III) + Co(III) + + Co(III) + 2 Fe(C 5 5 ) 2 Co(II) Fe(C 5 5 )

42 R R Cat. Me Me Dehydrogenation p Co Co R Me xygenation 41

43 42

44 43

45 44

46 45

47 46

48 47

49 48

50 49

51 µ 50

52 µ 51

53 µ 52

54 µη η µ µ µ 53

55 γ µ 54

56 π 55

57 α 56

58 57

59 π 58

60 π π 59

61 α α π 60

62 é 61

63 62

64 γ 63

65 64

66 µ 65

67 ü ü 66

68 67

69 π é 68

70 69

71 µ 70

72 µ 71

73 γ 72

74 73

75 74

76 75

77 76

78 π 77

79 78

80 79

81 π π 80

82 81

83 82

84 π π 83

85 84

86 85

87 π 86

88 µ 87

89 88

90 α 89

91 π 90

92 91

93 92

94 93

95 ü 94

96 95

97 96

98 π 97

99 98

100 99

101 100

102 101

103 102

104 I 103

105 ü 104

106 105

107 106

6 2 T γ T B (6.4) (6.1) [( d nm + 3 ] 2 nt B )a 3 + nt B da 3 = 0 (6.9) na 3 = T B V 3/2 = T B V γ 1 = const. or T B a 2 = const. (6.10) H 2 = 8π kc2

6 2 T γ T B (6.4) (6.1) [( d nm + 3 ] 2 nt B )a 3 + nt B da 3 = 0 (6.9) na 3 = T B V 3/2 = T B V γ 1 = const. or T B a 2 = const. (6.10) H 2 = 8π kc2 1 6 6.1 (??) (P = ρ rad /3) ρ rad T 4 d(ρv ) + PdV = 0 (6.1) dρ rad ρ rad + 4 da a = 0 (6.2) dt T + da a = 0 T 1 a (6.3) ( ) n ρ m = n (m + 12 ) m v2 = n (m + 32 ) T, P = nt (6.4) (6.1) d [(nm + 32 ] )a

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