The effect of complexation on the rates of electron transfer of iron porphyrins

A study has been made of the heterogeneous rate constants of iron porphyrins with pyridines and other nitrogenous base ligands. A direct relationship between the pK_a of the base and the rate constant has been found with a few exceptions. The measurements were by cyclic voltammetry. The larger the pK_a the stronger the complex between iron porphyrins and axial ligands. With strong ligands no ligand exchange or spin state change is expected. Both of these actions show the rate in agreement with the rates found in this work.     

Ligand structure, conformational dynamics, and excited-state electron delocalization for control of photoinduced electron transfer rates in synthetic donor-bridge-acceptor systems

Synthesis, ground-, and excited-state properties are reported for two new electron donor-bridge-acceptor (D-B-A) molecules and two new photophysical model complexes. The D-B-A molecules are [Ru(bpy)2(bpy-phi-MV)](PF6)4 (3) and [Ru(tmb)2(bpy-phi-MV)](PF6)4 (4), where bpy is 2,2'-bipyridine, tmb is 4,4',5,5'-tetramethyl-2,2'-bipyridine, MV is methyl viologen, and phi is a phenylene spacer. Their model complexes are [Ru(bpy)2(p-tol-bpy)](PF6)2 (1) and [Ru(tmb)2(p-tol-bpy)](PF6)2 (2), where p-tolyl-bpy is 4-(p-tolyl)-2,2'-bipyridine. Photophysical characterization of 1 and 2 indicates that 2.17 eV and 2.12 eV are stored in their respective (3)MLCT (metal-to-ligand charge transfer) excited state. These values along with electrochemical measurements show that photoinduced electron transfer (D*-B-A-->D (+)-B-A(-)) is favorable in 3 and 4 with DeltaG degrees(ET)=-0.52 eV and -0.62 eV, respectively. The driving force for the reverse process (D(+)-B-A(-) --> D-B-A) is also reported: DeltaG degrees(BET)=-1.7 eV for 3 and -1.5 eV for 4. Transient absorption (TA) spectra for 3 and 4 in 298 K acetonitrile provide evidence that reduced methyl viologen is observable at 50 ps following excitation. Detailed TA kinetics confirm this, and the data are fit to a model to determine both forward (k(ET)) and back (k(BET)) electron transfer rate constants: k(ET)=2.6 x 10(10) s(-1) for 3 and 2.8 x 10(10) s(-1) for 4; k(BET)=0.62 x 10(10) s(-1) for 3 and 1.37 x 10(10) s(-1) for 4. The similar rate constants k ET for 3 and 4 despite a 100 meV driving force (DeltaG degrees(ET)) increase suggests that forward electron transfer in these molecules in room temperature acetonitrile is nearly barrierless as predicted by the Marcus theory. The reduction in electron transfer reorganization energy necessary for this barrierless reactivity is attributed to excited-state electron delocalization in the (3)MLCT excited states of 3 and 4, an effect that is made possible by excited-state conformational changes in the aryl-substituted ligands of these complexes.     

Noncovalent assembly of a metalloporphyrin and an iron hydrogenase active-site model: photo-induced electron transfer and hydrogen generation

A noncovalent assembly of a pyridyl-functionalized hydrogenase active-site model complex and zinc tetraphenylporphyrin has been obtained and characterized. Upon light irradiation, fluorescence quenching by electron transfer was observed from the singlet excited state of the porphyrin to the diiron center, and the mechanism was verified by fluorescence lifetime and transient absorption spectroscopic measurements. In contrast to molecular dyads linked by covalent bonds, the assembled system was designed to avoid charge recombination via complex dissociation after photo-induced electron transfer. Visible light-driven hydrogen generation was observed from this self-assembled system. The assembling strategy employed in this study has the potential to be used for any other hydrogenase models in the future.     

Electron transfer rates and Franck–Condon factors: an application to the early electron transfer steps in photosynthetic reaction centers

Mechanistic aspects of some of the early electron transfer steps occurring in photosynthetic reaction centers are discussed. Starting from the normal modes of the redox cofactors involved in the electron transfer processes, we show how a series of quantities which regulate electron transfer rates, such as (i) the electron transfer active modes, (ii) the intramolecular reorganization energy, and (iii) the mutual couplings between the vibronic states of the donor and the acceptor, can be obtained and used to draw qualitative conclusions on ET rates.     

Effects of peripheral substituents and axial ligands on the electronic structure and properties of cobalt porphyrins

The effects of peripheral substituents and axial ligands (L) on the electronic structure and properties of cobalt tetraphenylporphyrin (CoTPP) have been studied using DFT methods. Various density functionals were tested, and the ground state of each system was determined by considering several possible low-lying states. The ground states of the fully fluorinated CoTPPF28(L)2 complexes with L = THF, Py, and Im were identified to be high-spin (4E(g)) by the meta-GGA functional tau-HCTH, which contains the kinetic energy density tau, in agreement with experimental measurements. All the pure GGA functionals, including the recently developed mPBE, OPBE, and HCTH/407, show more or less overestimation of the relative energies of the high-spin states. The energy gap between the 2A(1g) and 4E(g) states is insignificant (approximately 0.1 eV) and varies in the order L = Py < L = THF < L = Im. The results and their trend are consistent with 19F NMR studies which show partial population of the 4E(g) state in CoTPPF28(THF)2 and CoTPPF28(Py)2 and a complete conversion to the high-spin state in CoTPPF28(1-MeIm)2. Upon coordination by two very strong field axial CO ligands, CoTPPF28(CO)2 becomes low-spin, as in unligated CoTPPF(x). The influence of the peripheral substituents and axial ligands on the ionization potentials, electron affinities, and CoTPPF(x)-(L)2 binding strength was also investigated in detail.     

Estimates of electronic coupling for excess electron transfer in DNA

Electronic coupling V(da) is one of the key parameters that determine the rate of charge transfer through DNA. While there have been several computational studies of V(da) for hole transfer, estimates of electronic couplings for excess electron transfer (ET) in DNA remain unavailable. In the paper, an efficient strategy is established for calculating the ET matrix elements between base pairs in a pi stack. Two approaches are considered. First, we employ the diabatic-state (DS) method in which donor and acceptor are represented with radical anions of the canonical base pairs adenine-thymine (AT) and guanine-cytosine (GC). In this approach, similar values of V(da) are obtained with the standard 6-31G(*) and extended 6-31+ +G(**) basis sets. Second, the electronic couplings are derived from lowest unoccupied molecular orbitals (LUMOs) of neutral systems by using the generalized Mulliken-Hush or fragment charge methods. Because the radical-anion states of AT and GC are well reproduced by LUMOs of the neutral base pairs calculated without diffuse functions, the estimated values of V(da) are in good agreement with the couplings obtained for radical-anion states using the DS method. However, when the calculation of a neutral stack is carried out with diffuse functions, LUMOs of the system exhibit the dipole-bound character and cannot be used for estimating electronic couplings. Our calculations suggest that the ET matrix elements V(da) for models containing intrastrand thymine and cytosine bases are essentially larger than the couplings in complexes with interstrand pyrimidine bases. The matrix elements for excess electron transfer are found to be considerably smaller than the corresponding values for hole transfer and to be very responsive to structural changes in a DNA stack.     

A model for electrochemical electron transfer with strong electronic coupling

Electron exchange between a metal or semiconducting electrode and a solvated reactant is calculated by Green-function techniques. In the wide band approximation the time development of a system prepared in a definite electronic state can be calculated exactly. The results are valid for all coupling strengths, and are applied both to photoexcited and to thermally-induced transfer.     

Tuning the electronic communication and rates of intramolecular electron transfer of dimers of trinuclear ruthenium clusters: bridging and ancillary ligand effects

Ten new bridged dimers of oxo-centered triruthenium clusters with CO and 4-(dimethylamino)pyridine (dmap), pyridine (py), or 4-cyanopyridine (cpy) as terminal ligands and pyrazine-d(4) (d(4)-pz), 2,5-dimethylpyrazine (dmpz), 2-methylpyrazine (mpz), and 2-chloropyrazine (clpz) as bridging ligands were prepared. The carbonyl stretching frequency, nu(CO), was used as a probe for infrared spectroelectrochemical measurements. In the neutral and doubly reduced states, a single band was observed for each of the dimers, with a shift in frequency due to the oxidation state of the triruthenium clusters. In the singly reduced state, a range of nu(CO) line shapes was observed, depending on the nature of the ligands, from two bands centered at the frequencies of the bands of the neutral and doubly reduced species to one broad band at the average of these two frequencies. By synthesizing new combinations of bridging and ancillary ligands, electronic communication between two bridged triruthenium clusters was effectively tuned, and electron-transfer rates were estimated by IR spectral line-shape analysis. In dimers bridged by the asymmetric ligand mpz, it was possible through selective isotope labeling of one CO ligand to observe "mixed-valence isomers," the two alternate charge distributions of a mixed-valence complex.     

Estimation of electronic coupling for intermolecular electron transfer from cross-reaction data

Sixty-five electron-transfer reactions including 27 new 0, +1 couples have been added to our data set of cross-reactions between 0 and +1 couples, bringing it to 206 reactions involving 72 couples that have been studied by stopped-flow kinetics in acetonitrile containing supporting electrolyte at 25 degrees C, formal potentials determined by cyclic voltammetry, and analyzed using Marcus cross-rate theory. Perhaps surprisingly, a least-squares analysis demonstrates that intrinsic rate constants exist that predict the cross-rate constants to within a factor of 2 of the observed ones for 93% of the reactions studied, and only three of the reactions have a cross-rate constant that lies outside of the factor of 3, that corresponds to a factor of 10 uncertainty in the rate constant for an unknown couple. Many triarylamines, which have very high intrinsic reactivity, are included among the newly studied couples. The enthalpy contribution to the Marcus reorganization energy, lambda'v, has been calculated for 46 of the couples studied, at the (U)B3LYP/6-31+G (or for the larger and lower barrier compounds, at the less time-consuming (U)B3LYP/6-31G) level. In combination with a modified Levich and Dogodnadze treatment that assumes that the rate constant is proportional to (KeHab2/lambda1/2) exp[-DeltaG/RT], this allows estimation of the electronic coupling (Hab) at the transition state for intermolecular electron transfer, (more properly H'ab, the product of the square root of the encounter complex formation constant times Hab) for these couples. Although the principal factor affecting intermolecular electron-transfer rate constants is clearly lambda, H'ab effects are easily detectable, and the dynamic range in our estimates of them is over a factor of 600.     

Rational design principle for modulating fluorescence properties of fluorescein-based probes by photoinduced electron transfer

Fluorescence properties of fluorescein-based probes are shown to be finely controlled by the rate of photoinduced electron transfer from the benzoic acid moiety (electron donor) to the singlet excited state of the xanthene moiety (electron acceptor fluorophore). The occurrence of photoinduced electron transfer is clearly evidenced by transient absorption spectra showing bands due to the radical cation of the electron donor moiety and the radical anion of the xanthene moiety, observed in laser flash photolysis experiments. The photoinduced electron transfer rates and the rates of back electron transfer follow the Marcus parabolic dependence of electron transfer rate on the driving force. Such a dependence provides for the first time a quantitative basis for a rational design principle which has high efficiency in modulating fluorescence properties of fluorescein-based probes.     

Electropolymerization of cobalt porphyrins and corroles for the oxygen evolution reaction

Developing large-scale electrocatalysts using molecular complexes for the oxygen evolution reaction (OER) is of great importance. Herein, four cobalt porphyrins and corroles are deposited on electrode substrates using a simple and fast electropolymerization method. Our results showed that Co-1-P@CC, formed by electropolymerizing Co tetrakis(p-N-pyrrolylphenyl)porphyrin (Co-1-P) on carbon cloth (CC), is the most active OER catalyst in the examined Co porphyrins and corroles in alkaline aqueous solutions by displaying an onset overpotential of 380 mV. Long-term electrolysis tests confirmed the stability of these electropolymerized films by functioning as OER electrocatalysts.     

Tuning the rate and pH accessibility of a conformational electron transfer gate

Methods to fine-tune the rate of a fast conformational electron transfer (ET) gate involving a His-heme alkaline conformer of iso-1-cytochrome c (iso-1-Cytc) and to adjust the pH accessibility of a slow ET gate involving a Lys-heme alkaline conformer are described. Fine-tuning the fast ET gate employs a strategy of making surface mutations in a substructure unfolded in the alkaline conformer. To make the slow ET gate accessible at neutral pH, the strategy involves mutations at buried sequence positions which are expected to more strongly perturb the stability of native versus alkaline iso-1-Cytc. To fine-tune the rate of the fast His 73-heme ET gate, we mutate the surface-exposed Lys 79 to Ala (A79H73 variant). This mutation also simplifies ET gating by removing Lys 79, which can serve as a ligand in the alkaline conformer of iso-1-Cytc. To adjust the pH accessibility of the slow Lys 73-heme ET gate, we convert the buried side chain Asn 52 to Gly and also mutate Lys 79 to Ala to simplify ET gating (A79G52 variant). ET kinetics is studied as a function of pH using hexaammineruthenium(II) chloride (a6Ru2+) to reduce the variants. Both variants show fast direct ET reactions dependent on [a6Ru2+] and slower gated ET reactions that are independent of [a6Ru2+]. The observed gated ET rates correlate well with rates for the alkaline-to-native state conformational change measured independently. Together with the previously reported H73 variant (Baddam, S.; Bowler, B. E. J. Am. Chem. Soc. 2005, 127, 9702-9703), the A79H73 variant allows His 73-heme-mediated ET gating to be fine-tuned from 75 to 200 ms. The slower Lys 73-heme (15-20 s time scale) ET gate for the A79G52 variant is now accessible over the pH range 6-8.     

Energy transfer rates for vibrationally excited gas-phase azulene in the electronic ground state

Gas-phase azulene molecules were prepared with 17200 cm^?1 vibrational energy in the S₀ state by laser excitation of the S₁ state and subsequent internal conversion. Rates of vibrational energy removal (for several collision partners) were determined from the decay of the CH-stretch fluorescence at 3.3 μm. A stepladder model indicates each azulene-azulene collision removes 3500 cm^?1 of vibrational energy.     

Novel spectral and electrochemical characteristics of triphenylamine-bound zinc porphyrins and their intramolecular energy and electron transfer

Porphine bearing triphenylamine (TPA) pendant groups and their zinc complexes, zinc meso-tetra-p-(di-p-phenylamino)phenylporphyrin (ZnTDPAPP) and zinc meso-tetra-p-(di-p-tolylamino)phenylporphyrin (ZnTDTAPP) are synthesized and their spectral and electrochemical characteristics are studied. Zinc meso-tetraphenylporphyrin (ZnTPP) and zinc meso-tetra-p-aminophenylporphyrin (ZnTAPP) are also used as reference complexes. The B and Q bands of ZnTDPAPP and ZnTDTAPP are located at higher wavelengths and the bandwidths become broader compared with those of ZnTPP and ZnTAPP, indicating the peripheral TPA affects the electronic configuration of zinc porphyrins. Upon excitation in CH2Cl2 at room temperature, the compounds exhibit intramolecular singlet energy transfer from the TPA to the porphyrin core, and emission from the porphyrins are observed. Both ZnTDPAPP and ZnTDTAPP are easier to be oxidized and harder to be reduced than ZnTPP, in agreement with the strong electron-donating effect of the TPA groups. Extra waves corresponding to the oxidation of TPA substituents are also observed. The cation radical ZnTDTAPP+* exhibits an absorption spectrum very different from the typical spectra for porphyrin cation radicals. The NIR absorption band at 1296 nm indicates the electron transfer occurs intramolecularly. The above results evince the ability of TPA to modulate the electronic structure of zinc porphyrins.     

Low-temperature electronic transport through macromolecules and characteristics of intramolecular electron transfer

Long-distance electron transfer (ET) plays an important part in many biological processes. Also, fundamental understanding of ET processes could give grounds for designing miniaturized electronic devices. So far, experimental data on the ET mostly concern ET rates which characterize ET processes as a whole. Here, we develop a different approach which could provide more information about intrinsic characteristics of the long-range intramolecular ET. A starting point of the studies is an obvious resemblance between ET processes and electric transport through molecular wires placed between metallic contacts. Accordingly, the theory of electronic transport through molecular wires is applied to analyze characteristics of a long-range electron transfer through molecular bridges. Assuming a coherent electron tunneling to be a predominant mechanism of ET at low temperatures, it is shown that low-temperature current-voltage characteristics could exhibit a special structure, and the latter contains information concerning intrinsic features of the intramolecular ET. Using the Buttiker dephasing model within the scattering matrix formalism, we analyze the effect of dephasing on the electron transmission function and current-voltage curves.     

Concatenation of reversible electronic energy transfer and photoinduced electron transfer to control a molecular piston

Reversible electronic energy transfer and photoinduced electron transfer conspire in the light-driven dethreading of a molecular piston, showing the potential of combining these processes in supramolecular systems.     

Possible mechanisms of intermolecular charge transfer and electron transfer processes in the excited electronic state

Mechanisms of intermolecular charge transfer and electron transfer processes in the electronically excited states of solute molecules have been discussed in relation to the exciplex formation and fluorescence quenching reactions in solution. A new model for the electron transfer process has been proposed and studied by the quantum mechanical method. Some naive and intuitive concepts of the electron transfer process have been given a more rigorous theoretical basis. An experiment which can test this model has been suggested. Furthermore, the possible connections among the very weak CT complex formation, exciplex formation and the electron transfer reaction have been discussed in general on the basis of the theoretical considerations.

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Zusammenfassung Mechanismen für den intermolekularen Ladungs- und Elektronenübergang bei gelösten Molekülen in elektronisch angeregten Zuständen werden im Zusammenhang mit der Bildung von Exiplexen und der Fluoreszenzlöschung diskutiert. Für den Elektronenübergang wird ein neues Modell vorgeschlagen, das quantenmechanisch untersucht wird. Dadurch wird einigen einfachen und intuitiven Vorstellungen zum Elektronenübergang eine breitere theoretische Grundlage gegeben. Zur Überprüfung des Modells wird ein Experiment vorgeschlagen. Ferner werden auf der Grundlage theoretischer Überlegungen mögliche Zusammenhänge zwischen der Bildung eines sehr schwachen charge transfef-Komplexes, der Bildung eines Exiplexes und dem Elektronenübergang diskutiert.

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Résumé Les mécanismes de transfert de charge intermoléculaire et de transfert d'électrons dans les états électroniques excités de molécules solutées sont discutés en relation avec la formation d'exciplex et les réactions d'extinction de fluorescence en solution. On propose et on étudie quantiquement un nouveau modèle pour les processus de transfert d'électrons. Il donne une base théorique plus rigoureuse à certains représentations naïves et intuitives du transfert d'électron. On suggère une expérience pour étudier la validité de ce modèle. Enfin les rapports possibles entre la formation de complexes CT très faibles, la formation d'exciplex et la réaction de transfert d'électrons a été discutée de façon générale sur la base de considérations théoriques.