Spin Chemistry: How magnetic fields affect chemical reactions
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1 Spin Chemistry: How magnetic fields affect chemical reactions Part I: Basic Mechanism and Examples Ulrich Steiner University of Konstanz 1
2 available from the Home Page of the Summer School - Summary of the Lecture - PDF File of Presentation - Recommended Reading 2
3 Contents of Part I Basic Paradigm of Spin Chemistry The Radical Pair Mechanism Experimental Examples 3
4 Magnetic field dependence of chemical equilibria? G A B G A G B A B Reaction coordinate 4
![Magnetic field dependent chemical equilibria Low-spin to high-spin conversion Temperature-driven spin-crossover phenomenon in the polymorphic compound Fe[p-IC6H4)B(3-Mepz)3]2 from](/docs-images/78/77727516/images/5-0.jpg "high-spin Fe(II) (colorless) to low-spin Fe(II) (purple). Single crystals of two polymorphs are alternately mounted on the fiber. (Reger, et al. Inorg. Chem. 2005, 44(6), 1852-1866).")
5 Magnetic field dependent chemical equilibria Low-spin to high-spin conversion Temperature-driven spin-crossover phenomenon in the polymorphic compound Fe[p-IC6H4)B(3-Mepz)3]2 from high-spin Fe(II) (colorless) to low-spin Fe(II) (purple). Single crystals of two polymorphs are alternately mounted on the fiber. (Reger, et al. Inorg. Chem. 2005, 44(6), ). 5
6 Magnetic shift of chemical equilibria G G A A G B B Reaction coordinate 6
7 Magnetic field effects on chemical kinetics? 7
8 8
9 Standard Scenario of a Magnetic Field Dependent Chemical Reaction in out 3 Spin-selective reaction channels out 4 out 1 out 2 Set of near-degenerate intermediate states differing in spin quantum number 9
10 10
11 Standard Scenario of a Magnetic Field Dependent Chemical Reaction in out 3 Spin-selective reaction channels out 4 out 1 out 2 Set of near-degenerate intermediate states usually of a radical pair differing in spin quantum number 11
12 Radicals. how they are formed 12
13 In chemical bonds electrons are paired stable chemical compounds are usually diamagnetic 13
14 Radicals can be formed by Homolytic bond cleavage reactions O O O O heat O O + O O benzoylperoxide benzoyloxy radicals Electron transfer reactions A + D A - + D + radical ions 14
15 Electronic excitation = creation of an electron/hole pair opens the way for photochemical creation of radical pairs S 2 S 1 2 S 0 15
16 Electronic excitation = creation of an electron/hole pair opens the way for photochemical creation of radical pairs T 3 S 2 T 2 S 1 2 T 1 S 0 16
17 Electronic excitation = creation of an electron/hole pair opens the way for photochemical creation of radical pairs T 3 S 2 T 2 S 1 2 T 1 S 0 17
18 Electronic excitation = creation of an electron/hole pair opens the way for photochemical creation of radical pairs T 3 IC s S 2 IC (internal conversion) s T 2 S 1 2 fluorescence 10-8 s IC 10-9 s ISC (intersystem crossing) 10-9 s phosphorescence IC s T 1 S 0 18
19 19
20 20
21 Radical pair formation and reaction in solution 21
22 in out 3 out 4 out 1 out 2 Set of near-degenerate intermediate states differing in spin quantum number 22
23 23
24 spin dependent energies exchange energy Zeeman energy O O... O O effective Spin Hamiltonian 24
25 Radical Pair Spin Hamiltonian H = J ( S S + 1/ ) 1 i i i( 1) j(2) S1DS 2 + µ BS1g1B + S A I + S C K S 2 µ C B 2 S S K 2 2 g 2 2 A B j I 0 j exchange interaction electron spin dipolar interaction electronic Zeeman interaction hyperfine interaction spin-rotational interaction J exchange integral; D zero-field splitting tensor; g 1(2) g-tensor of radical 1(2); Ai (Aj ) hyperfine coupling tensors on radical 1(2); C 1(2) spin-rotational coupling constant on radical 1(2); S, I, K operators of electroi spin, nuclear spin, molecular rotational momentum, respectively 25
26 a semiclassical view of spin motion from Schulten, K.; Wolynes, P. G. J. Chem. Phys. 1978, 68,
27 Evolution of singlet probability in a radical pair created with triplet spin correlation. The individual hyperfine couplings correspond to effective fields of B 1 = 11 G and B 2 = 18 G 27
28 pyrene,-dimethylaniline 28
29 relative triplet yield theoretical B 1/2 value: 2 B * 3( B 1 + B 2 2 ) representative hyperfine field in each radical ( I ) 2 B1,2 = Ai Ii i + 1 i(1,2) B i : 2.5 G 3.7 G B i : 9.1 G 4.6 G 8 G B i : 9.1 G 34.5 G 17 G B* = 7.7 G 59 G B* = 17.7 G B* = 61.8 G Weller and olting, CPL 96 (1983) 24 29
30 The Magnetic Compass in Birds Does it involve Spin Chemistry? 30
31 from C. Rodgers, PhD Thesis, Oxford
32 from C. Rodgers, PhD Thesis, Oxford
33 from C. Rodgers, PhD Thesis, Oxford
34 from C. Rodgers, PhD Thesis, Oxford
35 Radical pairs with large differences in g-factors 35
36 Vector representation of radical pair spin states (after Turro and Kräutler) 36
37 37
38 g g = 1.18 = 2.60 Ru H 3 C CH 3 3 4τ S 1 4τ S 38
39 CH 3 Ru H 3 C 3 4τ S 1 4τ S scavenge with EDTA 39
40 40
41 41
42 42
43 43
44 CH 3 Ru H 3 C p = phenanthroline b = bipyridine 44
45 Kinetic Time Resolution determined by the Larmor Clock!!! 3 RuL MV 2+ photoelectron transfer RuL MV + free radicals fit of k ce escape efficiency: η ce (B 0 ) RuL 3 3+ MV + p S,i k bet RuL MV 2+ & ρ = i [ H, ] ρ + Rˆ ρ + Kˆ ρ Zeeman int.act., g g Ru(III)spin relaxation : τ S reactivity : k ce, k bet k ce, k bet, τ s 45
46 CH 3 Ru H 3 C p = phenanthroline b = bipyridine 46
47 Ligands (bpy) 3 (bpy)2 (phen) (bpy) (phen)2 (phen)3 G 0 bet, ev ηce k ce, ns k bet, ns τ s, ps g 2 γ e B 0 3 4τ S 1 4τ S 47
48 Optically probing spin motion on the ps-timescale 48
49 P. Gilch, F.Pöllinger-Dammer, C. Musewald, M.E. Michel-Beyerle Institut für. Physikalische und. Theoretische. Chemie, TU München U. E. Steiner, Fachbereich Chemie Universität Konstanz Magnetic Field Effect on Picosecond Electron Transfer Science, 281, 1998, Fe C 2 H 5 + O fet Fc.. 1 (Ox + ) * 1 (Fc +.. Ox ) 3 (Fc +.. Ox ) hν Fc..Ox + bet Spin relaxation and magnetic-field driven spin conversion 49
50 0-1 O x + D M A (CH 3 ) W avelength [nm ] D elay [ps] 50 ormalized Difference Absorbance [a.u.] Absorbance [OD] Probe Pump 0-1 C2 H5 Fe 2 O x + F c W a ve le ng th [n m ] D e la y [p s] ormalized Difference Absorbance [a.u.] Absorbance [OD] Probe Pump fet Fc.. 1 (Ox + ) * 1 (Fc +.. Ox 3 ) (Fc +.. Ox ) hν Fc..Ox + bet Spin relaxation and magnetic-field driven spin conversion
51 ormalized Difference Absorbance [a.u.] T esla 8.5 Tesla 2 O x + D M A Absorbance [OD] Probe Pump W avelength [nm ] fet Fc.. 1 (Ox + ) * 1 (Fc +.. Ox ) 3 (Fc +.. Ox ) D elay [ps] hν Fc..Ox + bet Spin relaxation and magnetic-field driven spin conversion ormalized Difference Absorbance [a.u.] T e sla 3 T e sla 5 T e sla 7 T e sla 8.9 Tesla Absorbance [OD] 2 0 O x + F c Probe Pump W a ve le ng th [n m ] D e la y [p s] 51
52 MFE [a.u.] MFE [a.u.] Delay [ps] ormalized Difference Absorbance [a.u.] T e sla 3 T e sla 5 T e sla 7 T e sla 8.9 Tesla Absorbance [OD] 2 0 O x + F c W a ve le ng th [n m ] D e la y [p s] Fc.. 1 (Ox + ) * 1 (Fc +.. Ox ) hν Fc..Ox + fet bet Probe Pump 3 (Fc +.. Ox ) Spin relaxation and magnetic-field driven spin conversion Electron transfer rate constant k ET 1.3 ps -1 Spin relaxation time τ s of Fc ps 52
53 Excited State 1 Ox +*... Fc Radical Pair States Ox... Fc T + FET S 0.2 T k ET =(0.9 ps) k ET =(4.3 ps) T Ground State Ox +... Fc 53
54 + Fe τ s electron spin relaxation time 1 H MR T 1 T 1 = ms τ s = 5.0 ps first excited KD lowest KD from temperature dependence of τ 458 cm -1 s : Orbach Mechanism 54
55 ED of Part I 55
56 Spin Chemistry: How magnetic fields affect chemical reactions Part II: Further Mechanisms and Techniques Ulrich Steiner University of Konstanz Summer School Cargèse
57 Contents of Part II The Relaxation Mechanism RYDMR CIDP The Triplet Mechanism CIDEP Summer School Cargèse
58 The role of spin relaxation Example of a linked radical pair Summer School Cargèse
59 (p) S (n) + + (m) Ru (p) 4p-PTZ n-dq S 4p-PTZ Summer School Cargèse
60 photoexcitation (p) S (n) + + (m) Ru (p) 4p-PTZ n-dq S 4p-PTZ Summer School Cargèse
61 Intersystem crossing (p) S (n) + + (m) Ru (p) 4p-PTZ n-dq S 4p-PTZ Summer School Cargèse
62 spin conserving electron transfer 1 1 (p) S (n) + + (m) Ru (p) 4p-PTZ n-dq S 4p-PTZ Summer School Cargèse
63 (p) S (n) + + (m) 2 Ru spin conserving electron transfer 2 (p) 4p-PTZ n-dq S 4p-PTZ Summer School Cargèse
64 (p) S (n) + + (m) Ru (p) 4p-PTZ n-dq S 4p-PTZ Summer School Cargèse
65 (p) S (n) + + n-dq (m) spin forbidden back transfer Ru (p) S 4p-PTZ 4p-PTZ Summer School Cargèse
66 normalized transient absorbance 1,0 0,8 0,6 0,4 0,2 0,0 (n) n-dq (m) ns Ru 2 S (p) (p) 4p-PTZ S 4p-PTZ 0 mt 10 mt 24 mt 50 mt 100 mt 300 mt 600 mt 1900 mt Summer School Cargèse
67 3 CS(T + ) normalized transient absorbance ns 0 mt 10 mt 24 mt 50 mt 100 mt 300 mt 600 mt 1900 mt k S 1 CS fast k r k r onzero Field Ground State (S 0 ) 3 CS(T 0 ) 3 CS(T - ) Summer School Cargèse
68 3 CS(T + ) normalized transient absorbance ns 0 mt 10 mt 24 mt 50 mt 100 mt 300 mt 600 mt 1900 mt k S 1 CS fast k r k r onzero Field Ground State (S 0 ) 3 CS(T 0 ) 3 CS(T - ) normalized concentration of CSS ns Summer School Cargèse mt 10 mt 24 mt 50 mt 100 mt 300 mt 600 mt 1900 mt 13
69 contributions to k r DCA-POZ kt=0 DCA-PSZ kt=0 k-poz/dq+esdi+c 10 7 k-psz/dq+esdi+c' c POZ c' PSZ X = Se kr/s X = O Summer School Cargèse B o /mt 14
70 What are the contributions to the relaxation rate constant k r? Summer School Cargèse
71 Relaxation by the esdi mechanism X k r, esdi = k T T, esdi = 3 h γ r 2 2 e 3 0 r 3 M a1τ ω0τ1 a2τ ω ± τ 0 2 a 1 = 0.6, a 2 = 0.4 τ = D cm s 1 τ = D cm s 1 Summer School Cargèse
72 contributions to k r 10 7 DCA-POZ kt=0 DCA-PSZ kt=0 k-poz/dq k-psz/dq k-poz/dq+esdi+c k-psz/dq+esdi+c' c POZ c' PSZ k-esdi D=9E-7 k-esdi D=2E-6 k-esdi D=5E-6 k-esdi D=1E kr/s Summer School Cargèse B o /mt 17
73 3 CS(T + ) normalized transient absorbance ns 0 mt 10 mt 24 mt 50 mt 100 mt 300 mt 600 mt 1900 mt k S 1 CS fast k r k r onzero Field Ground State (S 0 ) 3 CS(T 0 ) 3 CS(T - ) normalized concentration of CSS ns Summer School Cargèse mt 10 mt 24 mt 50 mt 100 mt 300 mt 600 mt 1900 mt 18
74 Standard Scenario of a Magnetic Field Dependent Chemical Reaction in Only one highly selective reaction channel out out 1 Set of near-degenerate intermediate states differing in spin quantum number Summer School Cargèse
75 Summer School Cargèse
76 RYDMR Reaction Yield Detected Magnetic Resonance 21
77 RYDMR Reaction yield detected magnetic resonance Summer School Cargèse
78 X 3 M + H-Det 3 (MH Det ) MH-X detected escape product 1 (MH Det ) MH-Det 2-methylnaphthoquinone O O = M ao 3 S X = DMS spin probe O Okazaki, M.; Sakata, S.; Konaka, R.; Shiga, T. J. Chem. Phys. 1987, 86, Summer School Cargèse
79 X 3 M + H-Det 3 (MH Det ) MH-X 1 (MH Det ) MH-Det Okazaki, M.; Sakata, S.; Konaka, R.; Shiga, T. J. Chem. Phys. 1987, 86, Summer School Cargèse
80 X 3 M + H-Det 3 (MH Det ) MH-X 1 (MH Det ) MH-Det Okazaki, M.; Sakata, S.; Konaka, R.; Shiga, T. J. Chem. Phys. 1987, 86, Summer School Cargèse
81 X 3 M + H-Det 3 (MH Det ) MH-X 1 (MH Det ) MH-Det Okazaki, M.; Sakata, S.; Konaka, R.; Shiga, T. J. Chem. Phys. 1987, 86, Summer School Cargèse
82 A conceptual link between RYDMR and Relaxation Mechanism Summer School Cargèse
83 Zeeman-Energy B 0 hν Lorentzian line shape of spectral density of stochastic perturbation by bath modes (log scale) microwave spectral density Summer School Cargèse
84 kr/s -1 Summer School Cargèse
85 CIDP Chemically Induced Dynamic uclear Polarization Summer School Cargèse
86 Assignment of MR signals by chemical shifts and multiplet structure A F C B D E Summer School Cargèse
87 ChemMR H-1 Estimation 1.14 O O Estimation Quality: blue = good, magenta = medium, red = rough 4 3 PPM Summer School Cargèse
88 Summer School Cargèse
89 Ward, H. R. Acc. Chem. Res. 1972, 5, during reaction at higher T Summer School Cargèse 2007 after stopping reaction at lower T 34
90 energy in magnetic field β thermal equilibrium uclear Spin Polarisation α-polarisation β-polarisation α Summer School Cargèse
91 Mechanism of net CIDP formation in singlet radical pairs forming singlet products g 1 > g 2 Summer School Cargèse
92 Vector representation of radical pair spin states (after Turro and Kräutler) Summer School Cargèse
93 Summer School Cargèse
94 Mechanism of net CIDP formation in singlet radical pairs forming singlet products g 1 > g 2 Summer School Cargèse
95 Summer School Cargèse
96 Kaptein s sign rules net effect Γn ( i) = µε Ai + g absorption emission + µ : - ε : + - if triplet precursor if singlet precursor if cage product if escape product multiplet effect Γ me ( i, p) = µε A A i p J ip + E / A A/ E Summer School Cargèse
97 Summer School Cargèse
98 The Triplet Mechanism Summer School Cargèse
99 energy eigenstates of a triplet spin system at zero field and in high magnetic field magnetic field x Summer School Cargèse
100 Summer School Cargèse
101 Summer School Cargèse
102 Summer School Cargèse
103 Stochastic Liouville equation set of Euler angles relating molecular frame to laboratory frame Summer School Cargèse
104 Ar 3 P +hν 1 (Ar 3 P)* 3 (Ar 3 P) Ar 2 P + Ar Ar 3 P = P triphenyl phosphine Ar 3 P Sakaguchi, Y.; Hayashi, H. Journal of Physical Chemistry A 2004, 108, Summer School Cargèse
105 Ar 3 P +hν 1 (Ar 3 P)* 3 (Ar 3 P) Ar 2 P + Ar Ar 3 P Ar 3 P = P triphenyl phosphine Sakaguchi, Y.; Hayashi, H. Journal of Physical Chemistry A 2004, 108, Summer School Cargèse
106 Photoelectron Transfer Summer School Cargèse
107 Photoelectron Transfer Summer School Cargèse
108 CIDEP: chemically induced dynamic electron spin polarization of radicals 53
109 Summer School Cargèse
110 Electron spin polarization (CIDEP) Summer School Cargèse
111 Summer School Cargèse
112 Spinpolarization by d-type TM Summer School Cargèse
113 MIE magnetic isotope effect MARY magnetically affected reaction yield RYDMR reaction yield detected magnetic resonance CIDP chemically induced dynamic nuclear polarization CIDEP chemically induced dynamic electron polarization MR nuclear magnetic resonance Summer School Cargèse 2007 ESR electron spin resonance 58
114 Summer School Cargèse
Spin Chemistry: How magnetic fields affect chemical reactions
pin Chemistry: How magnetic fields affect chemical reactions Part I: Basic Mechanisms and Examples Ulrich teiner University of Konstanz 1 U.E. teiner ummer chool Cargèse 007 1 Abstract lide o. History
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