Shunichi Fukuzumi - Electron Transfer

1 Cover

2 Acknowledgments Acknowledgments The author gratefully acknowledges the contributions of his collaborators mentioned in the references. The author thanks Japan Science Technology Agency and the Ministry of Education, Culture, Sports, Science and Technology of Japan for the continuous support.

3 1 Introduction

4 2 Marcus Theory of Electron Transfer

5 3 Photosynthetic Reaction Center Models

6 4 Electron Donor–Acceptor Dyads

7 5 Supramolecular Electron Transfer 5.1 Cation–Anion Binding 5.2 π‐Complexes 5.3 Electron‐Transfer Switching 5.4 Dendrimers 5.5 Supramolecular Solar Cells

8 6 Effects of Metal Ions on Photoinduced Electron Transfer

9 7 Photoredox Catalysis7.1 Photocatalytic Oxygenation 7.2 Photocatalytic Oxibromination 7.3 Carbon Carbon Bond Formation 7.4 DNA Cleavage 7.5 Anti‐Markovnikov Hydroetherification 7.6 Photocatalytic Cycloaddition 7.7 Photocatalytic Hydrotrifluoromethylation 7.8 Photocatalytic Hydrogen Evolution

10 8 Hydrogen Storage 8.1 Interconversion Between Hydrogen and Formic Acid 8.2 Interconversion Between Hydrogen and NADH 8.3 Hydrogen Evolution from Alcohols 8.4 Hydrogen Evolution from Paraformaldehyde

11 9 Metal Ion‐Coupled Electron Transfer (MCET)9.1 MCET of O2 9.2 Binding Modes of Metal Ions 9.3 Self‐Organized MCET 9.4 Accelerating and Decelerating Effects of Metal Ions 9.5 Driving Force Dependence of MCET Rate Constants 9.6 MCET Coupled with Hydrogen Bonding 9.7 MCET Catalysis 9.8 MCET of Metal‐Oxo Complexes 9.9 PCET of Metal‐Oxo Complexes 9.10 Unified Mechanism of MCET and PCET of Metal‐Oxo Complexes 9.11 MCET of Metal‐Peroxo Complexes

12 10 Catalytic Reduction of O 2

13 11 Catalytic Oxidation of H 2O

14 12 Production of Hydrogen Peroxide from Water and Oxygen as a Solar Fuel

15 13 Production and Usage of Hydrogen Peroxide as a Solar Fuel in Seawater

16 14 Photosystem II Mimic

17 15 Conclusion and Perspective

18 References

19 Index

20 End User License Agreement

1 Chapter 1 Figure 1.1 Cofactors and structure of photosynthetic reaction center of purple...

2 Chapter 2 Figure 2.1 (a) Schematic diagram of photoinduced electron transfer of an elect...

3 Chapter 3 Figure 3.1 Driving force (−Δ G ET) dependence of intramolecular electron‐transfe... Figure 3.2 Edge‐to‐edge distance ( R ee) dependence of optimal electron‐transfer... Scheme 3.1 Multistep photoinduced electron transfer in a ferrocene‐ meso , meso ‐...

4 Chapter 4 Scheme 4.1 Formation of a long‐lived CS state of a zinc imidazoporphyrin–C 60d... Scheme 4.2 Formation of a long‐lived CS state of ZnPQ–AuPQ +in nonpolar so... Figure 4.1 Structure of a closely linked ZnCh–C 60dyad. Scheme 4.3 Zinc porphyrin–quinone linked dyads (ZnP– n –Q; n = 3, 6, 10) with hy... Figure 4.2 (a) X‐ray crystal structure of Acr +–Mes. (b) HOMO and (c) LUMO ... Figure 4.3 Transient absorption spectra of Acr +–Mes (5.0 × 10 −5M) i... Figure 4.4 (a) UV–vis spectral change in the steady‐state photolysis of a deae... Figure 4.5 (a) Diagram of the reaction cavity: (left) diagram around the N ‐met... Figure 4.6 Transmission electron microscope (TEM) images of (a) tAlMCM‐41 an... Figure 4.7 (a) Synthetic procedure of CNC–(H 2P) n. (b) TEM image of CNC–(H 2P) n. Figure 4.8 (a) Transient absorption spectra of (a) CNC–(H 2P) ntaken at 20 and ...

5 Chapter 5 Figure 5.1 (a) Proposed complex formation. (b) UV–vis absorption titration of ... Figure 5.2 Transient absorption spectra of C8and Py, in a 1 : 1 ratio at 5.0 ... Figure 5.3 Crystal structure of H 4DPP(FcCOO) 2viewed from different directions... Figure 5.4 (a) Absorption spectral changes observed over the course of a titra... Figure 5.5 Driving force dependence of log k ET(•) or k BET(♦) for intrasupram... Figure 5.6 Dependence of ln k ETon distance for intrasupramolecular electron t... Scheme 5.1 Supramolecular complex formation and photoinduced charge separation... Figure 5.7 UV–vis spectra of H 2TPPS 4−(2.0 × 10 −6M) in the presen... Figure 5.8 (a) Transient absorption spectra of H 2TPPS 4−(2.5 × 10 −5... Figure 5.9 EPR spectra of (a) (ZnTPPS 4−) ·+–Li +@C 60 ·−... Figure 5.10 Formation of supramolecular porphyrin complexes, 1‐M 4−/( 2‐Zn Figure 5.11 X‐ray crystal structure of the supramolecular complex 1‐Zn 4– Figure 5.12 Chemical structure of Ni 2‐CPD Py. Figure 5.13 Crystal structures of tubular assemblies of C 60⊂Ni 2‐CPD Py. Hydroge... Figure 5.14 Supramolecular formation and photoinduced charge separation betwee... Figure 5.15 (a) Transient absorption spectra of Ni 2‐CPD Py(OC 6) with Li +@C 6... Scheme 5.2 Energy diagram for Li +@C 60⊂Ni 2‐CPD Py(OC 6); broken arrow: minor ... Figure 5.16 A porphyrin tripod and the reference dimer and monomer. Scheme 5.3 Formation of a supramolecular complex between TPZn 3and PyC 60. Figure 5.17 (a) UV–vis spectral changes upon addition of PyC 60(0–48 μM) to a Figure 5.18 Differential transient absorption spectra of (a) TPZn 3(7.0 × 10 –6... Scheme 5.4 Energy diagram for photodynamics of (a) TPZn 3and (b) MPZn in the p... Scheme 5.5 Photoinduced electron transfer in a π‐complex between a free base c... Figure 5.19 (a) Optimized structure of H 4DPOx–AcH +by DFT calculation. (b)... Scheme 5.6 Energy diagram of photoinduced electron transfer of the H 4DPOx–AcH +...Figure 5.20 (a) Plot of ln( k BET T 1/2) vs. T −1for the intramolecular BET ...Figure 5.21 Marcus driving force (−Δ G ET) dependence of the ET rate constants (...Figure 5.22 (a) Supramolecular nanohybrids of porphyrin–peptide hexadecamer [P...Figure 5.23 (a) Spectroscopic changes observed when TTF‐C4P (30 μM) is treated...Figure 5.24 (a) Single crystal X‐ray structure of the supramolecular donor–acc...Scheme 5.7 Chemical structures of TTF‐C4P and BIQ 2+salts, and their propo...Scheme 5.8 Ion‐mediated electron‐transfer reactions of a supramolecule between...Figure 5.25 (a) Near‐IR absorption spectral change in Cl −‐promoted elect...Figure 5.26 (a) EPR spectrum of the products of electron transfer from TTF‐C4P...Figure 5.27 Single crystal X‐ray structure of the product of electron transfer...Figure 5.28 Change in absorbance at 1035 nm seen upon the addition of increasi...Figure 5.29 A supramolecular complex between a zinc porphyrin dendrimer [D(ZnP...Figure 5.30 (a) Transient absorption spectra of D(ZnP) 16(2.3 × 10 −5M) ...Figure 5.31 (a) Insertion of C 60between the porphyrin rings of H 2PC15MPC and ...Figure 5.32 Illustration of the preparation of the OTE/SnO 2/(H 2PC15MPC+C 60) me...Figure 5.33 (A) Photocurrent action spectra of OTE/SnO 2/(H 2PC n MPC+C 60) melectr...Figure 5.34 Supramolecular organization between porphyrins and fullerenes with...Figure 5.35 (A) The photocurrent action spectra (IPCE vs. wavelength) of (a) (...Scheme 5.9 Schematic illustration of photocurrent generation mechanism of OTE/...Figure 5.36 Porphyrin dendrimers employed for construction of supramolecular s...Figure 5.37 TEM images of (a) Li +@C 60/ZnTPPS 4−and (b) Li +@C 60/HFigure 5.38 Schematic image of photoelectrochemical cell of OTE/SnO 2/MTPPS 4−...Figure 5.39 Photocurrent action spectra of OTE/SnO 2/(ZnTPPS 4−/Li +@C 6...

6 Chapter 6Scheme 6.1 Energy diagram and photodynamics of a zinc porphyrin–naphthalenedii...Scheme 6.2 Photodynamics of a ferrocene–anthraquinone dyad (Fc–AQ) (a) in the ...Figure 6.1 Fluorescence responses ( I / I 0at 610 nm) of ZnP–CONH–Qa...