Table 1 Spectroscopic and ET kinetic dataa and the LZ parametersb for mixed-valence complexes [EE′–(ph)n–EE′]+ (E E′ = O or S and n = 1–3)c.
From: Crossover between the adiabatic and nonadiabatic electron transfer limits in the Landau-Zener model
[EE′–ph–EE′]+ | [EE′–(ph)2–EE′]+ | [EE′–(ph)3–EE′]+ | |||||||
|---|---|---|---|---|---|---|---|---|---|
[OO] | [OS] | [SS] | [OO] | [OS] | [SS] | [OO] | [OS] | [SS] | |
rc–cd | 11.24 | 11.7 | 12.24 | 15.44 | 15.9 | 16.44 | 19.74 | 20.2 | 20.74 |
EIT (cm−1) | 4240(12) | 3440(4) | 2650(9) | 8300(8) | 6536(7) | 4830(12) | 12,405(30) | 7406(20) | 6210(15) |
εIT (M−1cm−1) | 1470(33) | 3690(93) | 12,350(80) | 201(12) | 715(9) | 1614(20) | 52(4) | 224(12) | 315(8) |
Δν1/2 (cm−1) | 4410(63) | 3290(46) | 1766(68) | 5183(60) | 6338(70) | 5231(43) | 3013(46) | 4210(32) | 4426(28) |
Hab (cm−1) | 589(8) | 726(5) | 856(9) | 190(7) | 354(9) | 415(8) | 63(2) | 126(5) | 135(4) |
λ/4 (cm−1) | 1060(3) | 860(1) | 663(0) | 2075(2) | 1634(2) | 1206(3) | 3101(8) | 1850(5) | 1550(4) |
ΔG* (cm−1) | 581(6) | 287(4) | 83(7) | 1889(4) | 1299(10) | 827(6) | 3038(54) | 1736(12) | 1414(10) |
(λ/4 − Hab) | 471(11) | 134(6) | −193(0) | 1885(9) | 1280(11) | 791(11) | 3038(10) | 1724(10) | 1415(8) |
ket(ad) (s−1) | 3.0(1) × 1011 | 1.4(0) × 1012 | 3.4(1) × 1012 | 4.1(1) × 108 | 9.3(3) × 109 | 9.2 (3) × 1010 | 2.3(3) × 105 | 5.5(1) × 108 | 3.0(2) × 109 |
ket(nonad) (s−1) | 7.3(1) × 1011 | 3.2(0) × 1013 | 1.4(1) × 1014 | 4.0(2) × 108 | 1.3(2) × 1010 | 1.7(1) × 1011 | 2.5(5) × 105 | 5.0(2) × 108 | 2.9(1) × 109 |
νel (s−1)e | 1.2(1) × 1014 | 2.1(1) × 1014 | 3.3(1) × 1014 | 9.1(4) × 1012 | 3.6(2) × 1013 | 5.7(2) × 1013 | 8.3(5) × 1011 | 3.9(4) × 1012 | 5.3(4) × 1012 |
γ | 1.95 | 3.29 | 5.26 | 0.15 | 0.57 | 0.91 | 0.013 | 0.061 | 0.084 |
P0 | 1 | 1 | 1 | 0.60 | 0.97 | 1 | 0.076 | 0.32 | 0.41 |
κel | 1 | 1 | 1 | 0.75 | 0.98 | 1 | 0.14 | 0.48 | 0.58 |
