Читать книгу Electron Transfer - Shunichi Fukuzumi - Страница 3
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Оглавление1 Chapter 1Figure 1.1 Cofactors and structure of photosynthetic reaction center of purple...
2 Chapter 2Figure 2.1 (a) Schematic diagram of photoinduced electron transfer of an elect...
3 Chapter 3Figure 3.1 Driving force (−ΔG 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 4Scheme 4.1 Formation of a long‐lived CS state of a zinc imidazoporphyrin–C60 d...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–C60 dyad. 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 × 10−5 M) 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–(H2P) n . (b) TEM image of CNC–(H2P) n .Figure 4.8 (a) Transient absorption spectra of (a) CNC–(H2P) n taken at 20 and ...
5 Chapter 5Figure 5.1 (a) Proposed complex formation. (b) UV–vis absorption titration of ...Figure 5.2 Transient absorption spectra of C8 and Py, in a 1 : 1 ratio at 5.0 ...Figure 5.3 Crystal structure of H4DPP(FcCOO)2 viewed 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 ET on distance for intrasupramolecular electron t...Scheme 5.1 Supramolecular complex formation and photoinduced charge separation...Figure 5.7 UV–vis spectra of H2TPPS4− (2.0 × 10−6 M) in the presen...Figure 5.8 (a) Transient absorption spectra of H2TPPS4− (2.5 × 10−5...Figure 5.9 EPR spectra of (a) (ZnTPPS4−)·+–Li+@C60 ·−...Figure 5.10 Formation of supramolecular porphyrin complexes, 1‐M4−/(2‐ZnFigure 5.11 X‐ray crystal structure of the supramolecular complex 1‐Zn4– Figure 5.12 Chemical structure of Ni2‐CPDPy.Figure 5.13 Crystal structures of tubular assemblies of C60⊂Ni2‐CPDPy. Hydroge...Figure 5.14 Supramolecular formation and photoinduced charge separation betwee...Figure 5.15 (a) Transient absorption spectra of Ni2‐CPDPy(OC6) with Li+@C6...Scheme 5.2 Energy diagram for Li+@C60⊂Ni2‐CPDPy(OC6); broken arrow: minor ...Figure 5.16 A porphyrin tripod and the reference dimer and monomer.Scheme 5.3 Formation of a supramolecular complex between TPZn3 and PyC60.Figure 5.17 (a) UV–vis spectral changes upon addition of PyC60 (0–48 μM) to a Figure 5.18 Differential transient absorption spectra of (a) TPZn3 (7.0 × 10–6...Scheme 5.4 Energy diagram for photodynamics of (a) TPZn3 and (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 H4DPOx–AcH+ by DFT calculation. (b)...Scheme 5.6 Energy diagram of photoinduced electron transfer of the H4DPOx–AcH+...Figure 5.20 (a) Plot of ln(k BET T 1/2) vs. T −1 for the intramolecular BET ...Figure 5.21 Marcus driving force (−ΔG 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 BIQ2+ 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 × 10−5 M) ...Figure 5.31 (a) Insertion of C60 between the porphyrin rings of H2PC15MPC and ...Figure 5.32 Illustration of the preparation of the OTE/SnO2/(H2PC15MPC+C60) m e...Figure 5.33 (A) Photocurrent action spectra of OTE/SnO2/(H2PCnMPC+C60) m electr...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+@C60/ZnTPPS4− and (b) Li+@C60/HFigure 5.38 Schematic image of photoelectrochemical cell of OTE/SnO2/MTPPS4−...Figure 5.39 Photocurrent action spectra of OTE/SnO2/(ZnTPPS4−/Li+@C6...
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 0 at 610 nm) of ZnP–CONH–Q a...
7 Chapter 7Scheme 7.1 Photocatalytic reaction of an electron donor (D) and an acceptor (A...Scheme 7.2 Photocatalytic oxygenation of anthracene with O2 using Acr+–Mes...Scheme 7.3 Photocatalytic oxygenation of AnO2 to anthraquinone with Acr+ ·...Scheme 7.4 Photocatalytic [2 + 2] cycloaddition of O2 to tetraphenylethylene (...Scheme 7.5 Photocatalytic cis–trans isomerization of stilbene with Acr+–Me...Scheme 7.6 Reaction scheme of photocatalytic oxygenation of p‐xylene and forma...Scheme 7.7 Photocatalytic mechanism of oxygenation of toluene derivatives (R‐CScheme 7.8 Photocatalytic mechanism of oxygenation of cyclohexane with Acr+...Scheme 7.9 Photocatalytic mechanism of bromination of aromatic compounds with ...Scheme 7.10 Photocatalytic dimerization of 9,10‐dimethylanthracene with Acr+...Figure 7.1 (a) Transient absorption spectra in PhCN observed in photoinduced E...Scheme 7.11 Photocatalytic oligomerization of C60 with Acr+–Mes.Scheme 7.12 Photocatalytic DNA cleavage with Acr+–Mes.Figure 7.2 Agarose gel electrophoresis of photoinduced cleavage of supercoiled...Scheme 7.13 Photocatalytic cycle for intramolecular anti‐Markovnikov hydroethe...Scheme 7.14 Photocatalytic cycle of intermolecular cycloaddition between β‐met...Scheme 7.15 Photocatalytic cycle of anti‐Markovnikov alkene hydroacetoxylation...Scheme 7.16 Photocatalytic cycle of trifluoromethylation of alkenes.Figure 7.3 Time dependence of hydrogen evolution under steady‐state irradiatio...Scheme 7.17 Mechanism of photoinduced reduction of Acr+–Mes with NADH.Scheme 7.18 PCET production of H2 with Acr·–Mes on PtNPs.Scheme 7.19 Structure of QuPh+–NA and the overall catalytic cycle for the ...Figure 7.4 Photocatalytic production of H2 from oxalate with QuPh+–N incor...Scheme 7.20 The catalytic cycle for the photocatalytic hydrogen evolution with...
8 Chapter 8Figure 8.1 ORTEP drawing of [IrIII(Cp*)(4,4′‐OMe‐bpy)(OH2)](OTf)2 (3·(OTf)2) w...Scheme 8.1 Catalytic cycle of the reduction of CO2 with H2 using [IrIII(Cp*)(4...Scheme 8.2 Acid–base equilibria of iridium aqua complexes (4–6).Figure 8.2 ORTEP drawing of 2. Hydrogen atoms are omitted for clarity. Selecte...Scheme 8.3 Catalytic cycle of the reduction of CO2 with H2 using [IrIII(Cp*)(4...Figure 8.3 pH Dependence of the formation rate (TOF) of formate in the catalyt...Figure 8.4 pH Dependence of the H2 evolution rate (TOF) in the catalytic hydro...Figure 8.5 Plot of TOF vs. concentration of HCOOH and HCOOK mixture (HCOOH/HCO...Scheme 8.4 Catalytic cycle of the decomposition of HCOOH using [IrIII(Cp*)(4–(...Scheme 8.5 A dinuclear Ir(Cp*) complex with 4,4′,6,6′‐tetrahydroxy‐2,2′‐bipyri...Figure 8.6 Crystal structure of [{Ir(Cp*)(Cl)}2(thbpym)]2+ [370]. CH bond...Scheme 8.6 Catalytic mechanism for interconversion between NADH and H2 with wa...Figure 8.7 Plot of TOF for catalytic hydrogen evolution vs. the concentration ...Figure 8.8 pH Dependence of the rate (TOF) of H2 evolution in the oxidation of...Figure 8.9 Plot of TOF vs. the concentration of NAD+ in the catalytic hydr...Scheme 8.7 Formation of a hydride complex 7 in the hydrogenation of 6 with ali...Figure 8.10 Change in absorbance at λ = 350 nm due to formation of the hy...Scheme 8.8 Catalytic cycle of hydrogen evolution from ethanol using [IrIII(Cp* Scheme 8.9 Photoconversion from a hydride complex 7 to 9.Figure 8.11 Time course of hydrogen evolution from 2‐propanol (4.3 M) catalyze...Scheme 8.10 Catalytic cycles for decomposition of paraformaldehyde to H2 and f...
9 Chapter 9Figure 9.1 ESR spectra of O2·−/M2+ complexes (M2+ = Mg2+, CaFigure 9.2 (a) ESR spectrum observed after irradiation of an 17O (40%) oxygen‐...Scheme 9.1 M n+‐promoted electron transfer from (TPP)Co to O2.Figure 9.3 Plots of log k et vs. ΔE in M n+‐promoted electron transfer from ...Scheme 9.2 M n+‐promoted electron transfer from (TPP)Co to Q.Figure 9.4 Plots of log k et vs. ΔE in electron transfer from (TPP)Co to O2, pr...Figure 9.5 UV–visible absorption spectra of PQ (1.2 × 10−4 M) in the pre...Figure 9.6 (a) UV–visible absorption spectra of PTQ (2.0 × 10−3 M) in th...Figure 9.7 (a) EPR spectrum of PQ·− produced by photoinduced electron tr...Figure 9.8 (a) EPR spectrum of PTQ·− produced by photoinduced electron t...Figure 9.9 CVs of PQ (1.5 × 10−3 M) (a) in the absence of metal ion, and...Figure 9.10 Dependence of the positive shift in E red (ΔE red) of PQ in the pres...Figure 9.11 Plots of E red of PQ (○) and PTQ (Δ) in the presence of M n+ (2....Scheme 9.3 Sc3+‐promoted electron transfer from (TPP)Co to PQ.Figure 9.12 Dependence of k obs on [Sc(OTf)3] for electron transfer from (TPP)C...Scheme 9.4 M n+‐promoted electron transfer from (AcrH)2 to PTQ in MeCN.Figure 9.13 Dependence of k obs on [M n+] for the electron transfer from (Ac...Figure 9.14 (a) Dependence of k obs on [Sc(OTf)3] for electron transfer from Ir...Figure 9.15 EPR spectra of an EtCN solution of Ir(ppy)3 (2.3 × 10−4 M) a...Scheme 9.5 Proportionation equilibrium between QH2 and Q in the presence of ScFigure 9.16 Absorption spectral changes of a deaerated EtCN solution of QH2 (3...Figure 9.17 EPR spectra of a deaerated propionitrile solution of QH2 (3.2 × 10Scheme 9.6 Formation of a chiral assembly [(NQ·−)2–(Sc3+(R)‐pybox)2]Figure 9.18 (a) Positive‐ion ESI mass spectrum of an MeCN solution of NQ (3.0 ...Figure 9.19 Absorbance at 633 nm for cycles of ET reduction of a deaerated MeC...Figure 9.20 The optimized structure of [(Q·−)2–(Sc3+(R)‐pybox)2]+...Scheme 9.7 Sc3+‐promoted electron transfer from (AcrH)2 to TolSQ in MeCN.Figure 9.21 (a) EPR spectrum of TolSQ·−–Sc3+ produced by electron tr...Figure 9.22 Dependence of k et on [Sc3+] for electron transfer from (AcrH)2 Scheme 9.8 Two pathways in electron transfer from electron donors to TolSQ–Sc3...Figure 9.23 Plots of ln(k et T −1) vs. T −1 for electron transfer from...Scheme 9.9 M n+‐promoted intramolecular electron transfer in a ferrocene–na...Figure 9.24 (a) CV of Fc–NQ (5.0 × 10−4 M) in deaerated MeCN containing ...Figure 9.25 Plots of ΔE 1/2 vs. log [M n+] for the one‐electron reduction of...Figure 9.26 (a) EPR spectrum of Fc+–NQ·−/Sc3+ (9.1 mM) produced ...Figure 9.27 Plots of log k ET vs. −ΔG ET in M n+‐promoted intramolecular elec...Scheme 9.10 M n+‐promoted intramolecular electron transfer in a ferrocene–n...Figure 9.28 Plots of −RT ln(k ET[M n+]−1/2) vs. ΔG ET in M n+‐promot...Figure 9.29 (a) ORTEP drawing of Fc–Q. (b) Optimized structure of Ph–Q·− Scheme 9.11 Photoinduced electron transfer from Fc to Q in the Fc–Q dyad, foll...Figure 9.30 CVs of (a) Fc–Q (0.5 mM) and (b) Fc–(Me)Q (0.5 mM) in MeCN contain...Scheme 9.12 M n+‐promoted electron transfer from Fc to Q in Fc–Q and Fc–(Me...Figure 9.31 Plots of log k et vs. ΔE in M n+‐promoted electron transfer in F...Figure 9.32 Formation of a cycloadduct by the reaction of t‐BuBNAH and Q in th...Figure 9.33 Dependence of k obs on [Sc3+] for (a) the cycloaddition reactio...Scheme 9.13 (a) Cycloaddition and (b) hydride transfer pathways via M n+‐pr...Figure 9.34 Crystal structures of (a) [CuIIZnII(bdpi)(MeCN)2](ClO4)3·2MeCN and...Figure 9.35 CVs of (a) [CuZn(bdpi)(MeCN)2]3+ (1.0 mM) and (b) [Cu(MeIm(Py)Scheme 9.14 Formation of the O2·− complex with [ZnII(MeIm(Me)2)]2+.Figure 9.36 EPR spectra of (a) [ZnII(O2·−)(MeIm(Py)2)]+ and (b) [ZnI...Scheme 9.15 The catalytic cycle of the imidazolate‐bridged CuII–ZnII heterodin...Scheme 9.16 Disproportionation of Q·− with [CuZn(bdpi)(MeCN)2]3+.Figure 9.37 Dependence of E red of [(N4Py)FeIV(O)]2+ in MeCN at 298 K on lo...Scheme 9.17 Metal ion‐coupled electron‐transfer reduction of [(N4Py)FeIV(O)]2+...Figure 9.38 Plots of log k 1(circles) and log k 2 (squares) of MCET from ferro...Figure 9.39 (a) ORTEP‐style and (b) chemical structure of the Sc3+‐bound n...Scheme 9.18 Sc3+‐coupled electron‐transfer chain reactions for formation o...Figure 9.40 (a) UV–vis spectral changes showing the conversion from [(Bn‐TPEN)...Figure 9.41 DFT‐optimized structure of [(Bn‐TPEN)MnIV(O)−[Sc(OTf)3]2]2+, c...Figure 9.42 Dependence of E red of [(N4Py)MnIV(O)]2+ (black circles) and [(...Scheme 9.19 Oxidation of a cobalt(III) complex to a cobalt(IV)‐oxo‐metal ion c...Figure 9.43 Dependence of E red of [(N4Py)FeIV(O)]2+ on log [HOTf] (grey ci...Figure 9.44 Plots of k obs vs. [HOTf] (black circles) and [DOTf] (grey circles)...Figure 9.45 UV–vis spectral changes observed in the titration of [(N4Py)MnIV(O...Figure 9.46 Dependence of E red of [(N4Py)MnIV(O)]2+ on the concentration o...Figure 9.47 Plots of log k obs for oxidation of toluene and thioanisole derivat...Figure 9.48 Plots of log k ET for CH bond cleavage of toluene derivatives and ...Scheme 9.20 Unified mechanism of oxidation of toluene and thioanisol derivativ...Figure 9.49 Electron‐transfer driving force (−ΔG et) dependence of log k ox for ...Figure 9.50 UV–vis spectra of [(TMC)FeIII(O2)]–M n+ complexes (M n+ = ScFigure 9.51 Plot of hν max of [(TMC)FeIII(O2)]+–M n+ complexes vs. ...
10 Chapter 10Figure 10.1 Time profiles of formation of [Fe(C5H4Me)2]+ monitored at 650 ...Scheme 10.1 The catalytic cycle for the two‐electron reduction of O2 by Fe(C5HFigure 10.2 Selected distance (Å) in Co2(DPB), Co2(DPA), Co2(DPX), and Co2(DPD...Scheme 10.2 The catalytic mechanism of the four‐electron reduction of O2 by fe...Figure 10.3 (a) Time profiles of formation of [Fe(C5Me5)2]+ monitored by a...Scheme 10.3 Catalytic dehydration vs. oxygenation of the R group of AcrHR with...Scheme 10.4 Mechanism of the catalytic oxygenation of the R group of AcrHR by ...
11 Chapter 11Scheme 11.1 Catalytic cycle for thermal water oxidation with CAN using [(L)RuI...Scheme 11.2 Catalytic cycle for photodriven water oxidation by persulfate us...Scheme 11.3 Catalytic cycle for water oxidation by CAN with a RuIII‐aqua compl...Scheme 11.4 Catalytic cycle for photodriven water oxidation by persulfate with...Scheme 11.5 Catalytic cycle for photodriven water oxidation at pH 9.3 by per...
12 Chapter 12Figure 12.1 Structures of Co porphyrin catalysts for two‐electron reduction of...Scheme 12.1 Photocatalytic water oxidation by O2 to produce H2O2.Figure 12.2 (a) Time courses of H2O2 production under visible light irradiatio...Figure 12.3 A schematic drawing of (Fe x Co1−x )3[Co(CN)6]2 where x = 0, 0....Figure 12.4 Schematic representation of a two‐compartment cell employed in t...Figure 12.5 Production of H2O2 under photoirradiation of a two‐compartment cel...Scheme 12.2 Photocatalytic water oxidation by O2 to H2O by double photoexcitat...
13 Chapter 13Figure 13.1 Photocatalytic production of H2O2 from water and O2 using m‐WO3/FT...Figure 13.2 Time courses of H2O2 production with m‐WO3/FTO photoanode and CoII Figure 13.3 I–V (light grey) and I–P (dark grey) curves of the one...
14 Chapter 14Figure 14.1 Time courses of O2 evolution by X‐Q [0.50 mM; DDQ (black), BQ (sec...Scheme 14.1 Proposed mechanism of the photodriven water oxidation by DDQ with ...
